1c. Modul Struktur Atom KB 3

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KEGIATAN BELAJAR-3
TEORI ATOM MEKANIKA GELOMBANG
A.
Tujuan Antara
Bagian modul ini membahas struktur atom menurut mekanika
gelombang yang berdasarkan atas penyelesaian persamaan Schrdinger. Oleh
karena bersifat sangat matematis dan juga sangat rumit, maka hanya (cara
memperoleh) hasil akhirnya saja yang ditampilkan, yang darinya dengan
relatif mudah ketiga bilangan kuantum diturunkan. Dalam hal ini bukan
mustahil materi ini lebih bersifat pengayaan untuk lebih memahami teori
atom mekanika gelombang. O l e h
s e b a b
i t u
s e t e l a h
m e
n y e l e s a i k a n
K e g i a t a n
B e l a j a r - 3
i n i
d i h
a r a p k a n
A n d a
m a m p u :
m e m a h m i
b a h w a
k e t i g a
( n i l a i )
b i l a n g a n
k u a n t u m ,
n ,
!,
d a n
m !,
m u n c u l
s e c a r a
n a
t u r a l - m a t e m a t i s
s e b a g a i
k o n s e k u e n s i
p e
n y e l e s a i a n
p e r s a m a a n
S c h r d i n g e r
m e n e n t u k a n
h u b u n g a n
n u m e r i k
! y a n g
d i p
e r b o l e h k a n
u n t u k
s e t i a p
h a r g a
n
m e n e n t u k a n
h u b u n g a n
n u m e r i k
m ! y a n g
d i
p e r b o l e h k a n
u n t u k
s e t i a p
h a r g a
!
m e m a h a m i
b a h w a
s e t i a p
j e n i s
o r b i t a l
d
e n g a n
l a m b a n g
s u m b u
C a r t e s
m e r u p a k a n
r
e p r e s e n t a s i
d a r i
n u m e r i k
m ! t e r t e n t u .
m e l u k i s k a n
j e n i s
o r b i t a l - angular p, dan d.
menuliskan konfigurasi elektronik atom unsur dengan prinsip aufbau, aturan

Hund dan kaidah Pauli
menjelaskan bahwa urutan energi orbital menurut diagram aufbau hanya tepateksak untuk 20 atom pertam, selebihnya menurut urutan naiklnya nilai n.
melukiskan diagram orbital konfigurasi elektronik
menentukan tetapan perisai, ,
d a n
m u a t a n
i n t i
e f e k t
i f ,
Z e f .
B .
U r a i a n
M a t e r i - 3
3 . 1
K e l e m a h a n
T e o r i
A t o m
B o h r
K i t a
t e l a h
b e l a j a r
b a h w a
t e o r
i
a t o m
B o h r
b e r a n g k a t
d a r i
s p e k t r u m
a t
o m
h i d r o g e n
( m o d e l
1
p r o t o n
d e n g a n
1
e
l e k t r o n )
y a n g
d i a s o s i a s i k a n
d e n g a n
t r a
n s i s i
e l e k t r o n i k .
K i t a
tahu bahwa dua elektron atau
lebih saling tolak menolak seperti halnya proton dengan elektron saling
tarik menarik; maka jelas bahwa energi total bagi atom atau spesies
berelektron banyak tidak dapat dihitung menurut rumusan Bohr. Oleh karena
itu tanpa adanya modifikasi, spektrum spesies berelektron banyak (lebih
dari satu) tidak mungkin dijelaskan menurut ramalan teori atom Bohr.
Untuk spesies berelektron dua misalnya He, ternyata teori
atom Bohr tidak dapat dikembangkan. Bahkan sekalipun untuk atom hidrogen,
teori atom Bohr tidak pernah mampu menjelaskan munculnya gejala spektrum
lain yang disebabkan oleh adanya pengaruh medan magnet atau medan listrik
dari luar. Adanya pengaruh medan magnet dari luar (percobaan Stark) ataupun
medan listrik (percobaan Zeeman) ternyata menimbulkan terjadinya pemisahan
atau pembelahan (splitting) garis-garis spektrum (Gambar 3.1)
Banyak usaha telah dilakukan, namun Bohr tetap tidak
pernah mampu memperluas atau mengembangkan teorinya sehingga gagal dalam
usahanya menjelaskan spektrum spesies berelektron banyak, yakni terjadinya
pemisahan garis-garis spektrum oleh pengaruh medan magnit maupun medan
listrik dari luar, dan timbulnya variasi intensitas garis-garis spektrum.
Perlu dicatat bahwa dalam teorinya Bohr melakukan perhitungan-perhitungan
berdasarkan pada campuran antara mekanika klasik dengan teori kuantum.
Untuk itu kita perlu belajar lebih lanjut sebagimana diuraikan berikut ini.
3.2
Struktur Halus Spektrum
Oleh karena teori atom Bohr pada dasarnya selalu diingat
dan bahkan dijadikan titik tolak bagi pengembangan teori atom berikutnya,
maka sebelum melangkah lebih lanjut perlu diingat kembali pemikiranpemikiran mengenai atom seperti berikut ini.
(1).
Suatu kumpulan partikel-partikel atomik, seperti inti sebuah atom
hidrogen dan
sebuah elektron yang terikat, mempunyai energi terkuantisasi tertentu.
(2).
Energi suatu sistem secara keseluruhan tergantung atau dipengaruhi
oleh interaksi
antar partikel-partikel penyusunnya, tetapi sebagian dari energi ini
misalnya saja energi kinetik adalah bebas dari pengaruh interaksi antar
partikel-partikel tersebut.
(3).
Perubahan naik-turunnya energi suatu sistem yang disebabkan oleh
perubahan
interaksi antar partikel-partikel penyusunnya sering secara praktis
dinyatakan sebagai perubahan energi elektron-elektron dalam sistem ini.
Jadi dalam hal yang demikian ini, pembahasan lebih sering mengenai energi
elektron daripada energi sistem.

(4).
Dalam atom, energi elektron atau energi interaksi suatu sistem
bersifat terkuantisasi. Bohr melukiskan sifat kuantisasi ini dalam
hubungannya dengan momentum sudut elektron kedalam bentuk persamaan mvr = n
( EMBED Equation.3
) (n = 1, 2, 3,). Sebuah elektron dalam atom mungkin
mendapatkan atau melepaskan momentum sudut sebesar n unit (1 unit = EMBED
Equation.3
), dan tidak dikenal adanya perubahan momentum sudut dalam
pecahan unit.
Perubahan energi atau tegasnya energi transisi elektronik
yang diterangkan oleh Bohr ini relatif besar pada skala atomik. Dugaan
adanya sejumlah perubahan energi yang relatif lebih kecil tentu memerlukan
penjelasan teoritik tersendiri dan ini dibahas pada bagian berikut.
Dengan peralatan spektrofotometer yang lebih canggih,
garis-garis spektrum yang semula tampak dan diduga tunggal sebagaimana
teramati oleh Bohr, ternyata terdiri atas beberapa garis majemuk yang
sangat dekat satu sama lain. Oleh karena jarak pisah garis-garis majemuk
ini sangat dekat dan hanya terdeteksi oleh peralatan yang lebih canggih
yang artinya mempunyai daya resolusi tinggi, maka sesungguhnya kita
dihadapkan pada struktur halus garis spektrum atau the fine structure of
line or spectrum.
Telah dikemukakan oleh Bohr bahwa setiap garis spektrum
diasosiasikan dengan transisi elektron dari tingkat energi satu ke tingkat
energi yang lain yang masing-masing dinyatakan dengan harga n (yang
kemudian disebut sebagai bilangan kuantum). Untuk garis-garis majemuk yang
sangat lembut tersebut tentu memerlukan spesifikasi baru mengenai tingkattingkat energinya yang mempunyai perbedaan sangat kecil, jauh lebih kecil
daripada perbedaan energi antara tingkat-tingkat energi utama yang menunjuk
pada orbit elektron yang dikemukakan oleh Bohr.
Menghadapi hasil pengamatan baru ini, seorang ahli fisika
Jerman, Arnold Sommerfeld, mengemukakan asumsinya bahwa orbit elektron
tidak selalu berbentuk lingkaran seperti asumsi Bohr melainkan bentuk elips
juga dapat memenuhi rumusan momentum sudut elektron, mvr =
EMBED
Equation.3
. Dengan demikian, suatu objek misalnya elektron yang sedang
bergerak dalam bentuk orbit terhadap objek lain yaitu inti atom, terdiri
atas dua komponen energi yaitu energi yang berkenaan dengan gerak menyudutangular (Ea) dan energi yang berkenaan dengan gerak radial (Er). Seperti
ditunjukkan Gambar 3.2, gerak radial ini menunjuk pada gerak mendekat atau
menjauhnya objek elektron yang sedang bergerak menempuh orbit terhadap
objek inti atom sepanjang jari-jarinya. Jadi, energi total (Et) sistem ini
adalah Et = Ea + Er .
Bila orbit elektron berbentuk lingkaran, berarti Er
berharga nol karena tidak adanya perubahan jari-jari atau tidak ada
perubahan jarak antara inti sebagai titik pusat orbit dengan elektron
sepanjang orbitnya; dengan demikian, Bohr hanya mempertimbangkan energi
total (Et) saja.
Lebih lanjut Sommerfeld mampu merumuskan besaran Ea dan Er
untuk spesies satu elektron yang keduanya bersifat terkuantisasi; artinya,
harga keduanya dikontrol oleh bilangan-bilangan kuantum berinteger satu,
analog dengan bilangan kuantum yang diusulkan oleh Bohr. Jadi, ketiga
besaran energi tersebut, Et, Ea, dan Er, semuanya terkuantisasi, tetapi Er
ditentukan oleh Et dan Ea. Bilangan kuantum Bohr selanjutnya disebut
sebagai bilangan kuantum utama (n) yang diasosiasikan dengan energi kulit
utama elektron; sedangkan bilangan kuantum Sommerfeld disebut sebagai
bilangan kuantum azimut atau bilangan kuantum sekunder dengan notasi

l,
b e r h a r g a ,
0 ,
1 ,
2 ,
3 ,
. . .
( n
- 1 )
y a n g
s e r i n g
d e n g a n
e n e r g i
s u b
- k u l i t
e l e k t r o n .
P e r l u
d i c a t a t
b a h w a
u
n t u k
l =
0
b e r a r t i
o r b i t
e l e k t r o n
b e r b
e n t u k
l i n g k a r a n ,
s e d a n g k a n
u n t u k
l
(
1
o r b i t
e l e k t r o n
b e r b e n t u k
e l i p s
y a n
g
m a k i n
m e n y i m p a n g
d a r i
b e n t u k
l i n g k a r
a n
d e n g a n
m a k i n
b e s a r n y a
h a r g a
l.
D e n g a n
d e m i k i a n ,
n a i k n y a
e n e r
g i
e l e k t r o n i k
y a n g
s e s u n g g u h n y a
a d a l a h
e n e r g i
a t o m
a t a u
e n e r g i
s i s t e m ,
d a p a t
d e n g a n
n a i k n y a
e n e r g i
s u
b - k u l i t
y a n g
b e r a r t i
n a i k n y a
b i l a n g a n
k u a n t u m
s u b - k u l i t
a t a u
o rbit elip. Namun, karena
elektron hanya boleh mempunyai harga energi terkuantisasi tertentu, ini
berarti bahwa hanya ada sejumlah tertentu pula energi-energi sub-kulit yang
tersedia; dan dalam hal ini Sommerfeld mengemukakan hanya sejumlah subkulit yang diperlukan saja untuk menjelaskan spektrum halus garis-garis
majemuk yang teramati. Hasilnya dalam hubungannya dengan bilangan kuantum
utama, n, ditunjukkan oleh Tabel 3.1.
Tabel
3.1
Hubungan kulit utama dengan sub-kulit menurut
Sommerfeld
Kulit Utama Su b - k u l i t
( l)
( n
)
j u m l a h
m a c a m
h a r g a ,
0
( n
- 1 )
S i m b o l
1
1
0
1 s
( s h a r p )
2
2
0
2 s
1
2 p
( p r i n c i p l e )
3
3
0
3 s
1
3 p
2
3 d
( d i f f u s e )
4
4
0
4 s
1
4 p
2
4 d
3
4 f
( f u
n d a m e n t a l )
M e n u r u t
m o d e l
B o h r ,
t r a n s i s i
e l e k t r o n i k
y a n g
t e r a m a t i
p a d a
s p e k t r u m
g a r i s
m e n u n j u k
p a d a
p e r p i n d a h
a n
e l e k t r o n
a n t a r
t i n g k a t - t i n g k a t
e n e r
g i
u t a m a ,
n ,
m i s a l n y a
d a r i
n = 2
k e
n = 1 ,
s e d a n g k a n
m o d e l
S o m m e r f e l d
m e m u n g k i n k a
n
j u g a
t e r j a d i n y a
t r a n s i s i
e l e k t r o n i k
y a n g
m e l i b a t k a n
t i n g k a t
e n e r g i
s u b - k u l
i t ,
l,
y a n g
berasal dari kulit utama yang berbeda, misalnya
dari orbit ns ke orbit (n-1)s seperti 2s ke 1s, dari orbit np ke orbit
(n1)s seperti 2p ke 1s. Oleh karena perbedaan energi antara 2s dengan 2p
relatif jauh lebih kecil daripada perbedaan energi antara 2s dengan 1s
demikian juga antara 2p dengan 1s, maka kedua transisi elektronik ini
mempunyai energi yang hampir sama, sehingga dua garis spektrum yang
diasosiasikan dengan kedua transisi elektronik ini muncul sangat berdekatan
sesuai dengan pengamatan sebagai struktur halus garis-garis spektrum. Jadi
model Sommerfeld cukup beralasan dalam menjelaskan struktur halus spektrum
garis atom hidrogen walaupun transisi elektronik yang mungkin muncul
menurut rumusannya ternyata tidak semuanya teramati. Perluasan model atom
ini kemudian lebih dikenal sebagai model Bohr - Sommerfeld. Nah, sepahamkah
Anda dengan Sommerfeld?
3.3
Sifat Gelombang Partikel
Walaupun Bohr telah melukiskan struktur atom cukup rinci,
namun masih ada sesuatu yang hilang. Apanya yang hilang? Untuk ini perlu
kita tinjau kembali mengenai sifat cahaya. Para ilmuwan selalu saja
mendapat kesulitan dalam melukiskan sifat karakteristik cahaya. Banyak

percobaan dengan jelas menunjukkan bahwa cahaya bersifat gelombang, tetapi
percobaan lain menunjukkan bahwa cahaya bersifat sebagai partikel (yang
nantinya dikenal sebagai aliran foton yang membawa paket-paket energi atau
sejumlah energi diskret terkuantisasi), sebagaimana terjadi pada berbagai
jenis gejala dalam Tabel 3.2.
Tabel 3.2
Perbandingan konsistensi cahaya dalam berbagai gejala
Gejala Teori Gelombang Teori Partikel Difraksi Konsisten tidak konsisten
Refleksi, Refraksi Konsisten Konsisten Interferensi Konsisten tidak
konsisten Efek Fotolistrik tidak konsisten Konsisten Penyebaran energi
radiasi Konsisten Konsisten Polarisasi cahaya Konsisten tidak konsisten
Efek Compton tidak konsisten Konsisten
Nah, dari perbandingan
gejala-gejala tersebut dapat dipertimbangkan bahwa sifat cahaya atau energi
radiasi secara umum berhubungan dengan sifat gelombang dan sifat partikel
atau sering dikenal sebagai sifat mendua cahaya yaitu sifat gelombang partikel. Dalam hal seperti ini, sejumlah asumsi yang kemudian merupakan
dasar pengembangan teori kuantum dapat dirumuskan sebagai berikut.
(1).
Atom-atom berkelakuan sebagai osilator, menghasilkan gelombang
elektromagnetik dengan frekuensi gelombang yang karakteristik bagi atom
yang bersangkutan.
(2).
Energi tidak dibawa oleh gelombang itu sendiri melainkan oleh
foton yang
kecepatan alirnya diberikan oleh
intensitas gelombang yang bersangkutan.
(3).
Kecepatan pancaran gelombang oleh osilator-osilator menentukan
peluang
pancaran foton oleh sumbernya.
Ketiga asumsi tersebut dapat diringkas dalam bentuk (kuantum asli) seperti
yang diusulkan oleh Max Planck, yaitu bahwa osilator-osilator memancarkan
energi dalam bentuk kelipatan integral dari paket energi basis (yaitu
foton) sebagai E = nh n ( n
=
b i l a n g a n
k u a n t u m
a t a
u
d i s k r e t ,
d a n
n =
f r e k u e n s i
o s i l a t o r
) .
P a d a
t a h u n
1 9 2 4
s e o r a n g
f i s i k
a w a n
P r a n c i s ,
L o u i s
d e
B r o g l i e ,
m e n g u s
u l k a n
a l t e r n a t i f
l a i n
u n t u k
m e n j e l a s k a
n
r u m u s a n
B o h r
m e n g e n a i
m o m e n t u m
s u d u t
e l e k t r o n
y a n g
t e r k u a n t i s a s i ,
d e n g a n
m e
n g u b a h
e k s p r e s i
p e r s a m a a n
y a n g
b e r s a n g
k u t a n
( p e r s a m a a n
2 . 8 )
m e n j a d i
2 pr
=
E
M B E D
E q u a t i o n . 3
.
D a l a m
p e r s a m a a n
i n
i
t e r l i h a t
b a h w a
2 pr
t i d a k
l a i n
a d a l a h
k e l i l i n g
l i n g k a r a n
y a n g
o l e h
d e
B r o g l i
e
d i a s u m s i k a n
s e b a g a i
o r b i t
e l e k t r o n .
D e n g a n
d e m i k i a n ,
o r b i t
e l ektron juga bersifat
terkuantisasi. Mengapa orbit elektron ini ditentukan oleh harga-harga h, m,
dan n? Dalam hal ini de Broglie mengusulkan bahwa bila cahaya menunjukkan
sifat mendua gelombang - partikel, maka secara sama materi yang jelas
menunjukkan sifat partikel tentu juga mempunyai sifat gelombang. Pendapat
ini agak aneh kedengarannya bukan? Namun, sesungguhnya hal ini menunjukkan
sifat analogi yang benar-benar paralel; dasar pemikirannya dengan
mempertimbangkan momentum foton.
Oleh karena momentum partikel yang sedang bergerak
dinyatakan sebesar mv, maka sebuah foton yang tidak terdeteksi karena
terlalu kecil massanya mestinya tidak mempunyai momentum (nol). Namun,
kesimpulan yang terakhir ini tidaklah benar sebagaimana dibuktikan oleh
teori relativitas Einstein. Dengan mengingat kembali hubungan massa dengan

energi menurut Einstein, E = mc2, de Broglie merumuskan massa foton sebagai
m =
EMBED Equation.3
, dan substitusi energi ini menurut Planck
diperoleh:
m =
EMBED
Equation.3
atau
m =
EMBED Equation.3
...........
(3.1)
Jadi, massa foton berbanding terbalik dengan panjang gelombangnya atau
berbanding lurus dengan frekuensinya. Lebih lanjut, de Broglie menganggap
beralasan untuk berpikir mengenai panjang gelombang suatu partikel seperti
halnya panjang gelombang foton yang mempunyai kecepatan v. Oleh karena itu,
paralel dengan persamaan (3.1) diperoleh rumusan - persamaan (3.2):
m =
EMBED Equation.3
atau
l
=
E
M B E D
E q u a t i o n . 3
( d e n g a n
v
=
k e c e p a
t a n
p a r t i k e l )
. . . . . . .
( 3 . 2 )
D e n g a n
d e m i k i a n ,
p a r t i k e l
y a n
g
s e d a n g
b e r g e r a k
m e n u n j u
k k a n
s i f a t
g e l o m b a n g
y a n g
b e s a r n y a
b e r
b a n d i n g
t e r b a l i k
d e n g a n
m o m e n t u m
p a r t i
k e l
y a n g
b e r s a n g k u t a n .
U n t u k
m
yang sangat
kecil seperti partikel-partikel atomik atau partikel mikro dengan kecepatan
mendekati kecepatan cahaya, sifat gelombangnya menjadi sangat nyata. Akan
tetapi untuk partikel-partikel makro yang massanya besar, sifat gelombang
sangat jauh lebih kecil terlebih-lebih jika partikel ini mempunyai
kecepatan yang jauh lebih lambat daripada kecepatan cahaya seperti
diungkapkan pada contoh perhitungan berikut ini.
Contoh Soal
(1).
Hitung panjang gelombang elektron yang sedang bergerak dengan
kecepatan kira k i r a
1 %
k e c e p a t a n
c a h a y
a .
( 2 ) .
H i t u n g
p a n j a n g
g e l o m b a n g
s e b u
a h
b o l a
1 0
g
y a n g
s e d a n g
b e r g e r a k
d e n g
a n
k e c e p a t a n
5
m
p e r
d e
t i k .
P e n y e l e s a i a n
( 1 )
M e n u r u t
d e
B r o g l i e :
l
=
E M B E D
E q u a t i o n . 3
=
E M B
E D
E q u a t i o n . 3
=
2 , 4 3 . 1 0 - 1 0
m
=
2 4 3
p m
=
2 , 4 3
( b i l a n
g a n
i n i
b e r d i m e n s i
a t o m i k )
( 2 )
l
=
E M B E D
E q u a t i o n . 3
=
E M
B E D
E q u a t i o n . 3
=
1 , 3 2 3 . 1 0 - 3 2
m
B i l a n g a n
i n i
s u n g g u h
m e r u p a k a n
h a r g a
p a n j a n g
g e l o m b a n g
y a n g
s a n g a t
k e c i l
y a
n g
s u l i t
t e r d e t e k s i
d a n
t i d a k
m e m p u n y a
i
a p a p u n .
S e b a g a i
p e r b a n d i
n g a n ,
p a n j a n g
g e l o m b a n g
b e b e r a p a
o b j e k
y a n g
s e d a n g
b e r g e r a k
d a p a t
d i p e r i k s a
p
a d a
T a b e l
3 . 3 .
T a b e l
3 . 3
P a n j a n g
g e l o m b a
n g
b e b e r a p a
o b j e k
y a n g
s e d a n g
b e r g e r a k
P a r t i k e l
m a s s a
/
k g
k e c e p a t a n
/
m
s - 1
l /
p m
E l e k t r o n
d i p e r c e p a t
1 0 0
v o l t
9
, 1 1
x
1 0 - 3 1
5 , 9
x
1 0 6
1 2 0
E l e k t r o n
d i
p e r c e p a t
1 0 4
v o l t
9 , 2 9
x
1 0 - 3 1
5 , 9
x
1
0 7
1 2
P a r t i k e l
a
d a r i
n u k l i d a
R a
6 ,
6 8
x
1 0 - 2 7
1 , 5
x
1 0 7
6 , 6
x
1 0 - 1
P e l u r
u
k a l i b e r
2 2
1 , 9
x
1 0 - 3
3 , 2
x
1 0 2
1 , 1
x
1 0 - 3 3
B o l a
g o l f
0 , 0 4 5
3 0
4 , 9
x
10-34
Bola basket 0,140 25 1,9 x 10-34
EMBED Word.Picture.8
Gambar 3.3
Gambar menunjukkan sifat gelombang de Broglie
dalam orbit Bohr yang
(A)
berkelanjutan, ajeg serba terus tidak terhapus (standing wave),
bila jumlah gelombang (n) berupa bilangan bulat,
(B-D) terhapus, bila jumlah
gelombang (n) berupa bilangan pecahan.
Berdasarkan persamaan 2.8, persamaan 3.2 dapat diubah
menjadi 2 p r
=
n
l.
J a d i ,
l i n g k a r a n
o r b i
t
e l e k t r o n
t e r k u a n t i s a s i
d e n g a n
k e l i p a
t a n - k e l i p a t a n
i n t e g e r
d a r i
h a r g a
p a n j a
n g
g e l o m b a n g
e l e k t r o n
y a n g
b e r s a n g k u t a
n .
B e r b e d a
d e n g a n
B o h r
y a n g
m e m a n d a n g
e l e k t r o n
s e b a g a i
p a r t i k e l
y a n g
m e n g o r b
i t
m e n g e l i l i n g i
i n t i
a t o m ,
d e
B r o glie
memandang elektron sebagai gelombang atau bila bukan merupakan gelombang
murni, elektron dipandang sebagai gelombang yang berasosiasi dengan
partikel yang sangat kecil yang bergerak sangat cepat. Jadi, elektron oleh
de Broglie digambarkan sebagai gelombang ajeg - serba terus (standing wave)
dengan jejak melingkar tertutup tanpa ujung - pangkal seperti ditunjukkan
oleh Gambar 3.3(A).
Untuk memenuhi sifat standing wave ini, jelas bahwa jumlah
panjang gelombang harus terkuantisasi (n = 1, 2, 3, 4, .......). Bila
harga n berupa pecahan (misalnya 2,5; 3,5), maka sifat gelombang akan
menjadi terhapus (Gambar 3.3B-D). Perlu dicatat bahwa pada waktu itu belum
ada bukti eksperimen yang mendukung pandangan de Broglie, namun ternyata
bukti yang diperlukan kemudian menjadi kenyataan dalam waktu yang relatif
singkat sebagai konsekuensi logis pandangan tersebut.
Telah diketahui bahwa panjang gelombang elektron ternyata
kira-kira sama dengan panjang gelombang sinar-X. Dengan demikian, seberkas
sinar elektron, yang semula dipandang sebagai partikel, diharapkan akan
menghasilkan pola difraksi yang sama dengan pola difraksi yang dihasilkan
oleh sinar-X, yang membawa sifat gelombang. Kenyataannya memang demikian;
kira-kira tahun 1927, G. P. Thomson (anak dari J. J. Thomson) dapat
menunjukkan pola difraksi yang dihasilkan oleh elektron-elektron
berkecepatan tinggi pada lempeng aluminium yang ternyata sama dengan pola
difraksi yang dihasilkan oleh sinar-X yang pertama kali ditunjukkan oleh
Max Von Laue (1912). Jadi, tidak diragukan lagi bahwa elektron juga
berkelakuan sebagai gelombang seperti halnya sinar-X.
Nah, asumsi de Broglie bahwa partikel yang sedang bergerak
mempunyai sifat gelombang dan penemuan berikutnya bahwa elektron
menunjukkan sifat gelombang mengantar teori atom ke arah perkembangan yang
lebih modern yang kemudian dikenal sebagai teori atom mekanika gelombang.
Beberapa tokoh ilmuwan antara lain, L. de Broglie, Erwin Schrdinger, W.
Heisenberg dan Max Born, memberikan sumbangan yang paling banyak dalam
perkembangan teori atom mekanika gelombang ini. Dalam teori ini, elektron
diperlakukan sebagai gelombang daripada sebagai partikel. Tidak ada usaha
untuk membuat model visualisasi tentang atom, melainkan berupa deskripsi

matematik yang sangat kompleks, yang secara khusus dapat dipelajari dalam
buku-buku Mekanika Gelombang (Wave Mechanics) dan Kimia Kuantum (Quantum
Chemistry). Namun demikian, banyak kesimpulan yang diturunkan dari
mekanika gelombang dapat diungkapkan kedalam bentuk bahasa non-matematik
sebagaimana dibicarakan secara ringkas berikut ini.
Catatan:
J. J. Thomson (ayah), menemukan elektron sebagai partikel
(1895) dan memenangkan
hadiah Nobel
pada tahun 1906, sedangkan G. P. Thomson (anak) menunjukkan bahwa
elektron bersifat gelombang (1927) dan
memenangkan hadiah Nobel pada tahun 1937.
3.4
Prinsip Ketidak-pastian
Pada tahun 1927, Werner Heisenberg, seorang fisikawan
Jerman, mengemukakan suatu uncertainty principle atau asas ketidak-pastian
sehubungan dengan tindakan pengamatan terhadap perubahan kondisi objek yang
sedang diamati. Bila misalnya digunakan termometer untuk mengukur suhu
suatu objek, maka suhu objek akan berubah naik atau turun ketika terjadi
kontak antara objek dengan termometer tersebut. Tentu saja efek perubahan
suhu ini hanya signifikan bila jumlah objek sangat sedikit. Demikian juga
saat mengamati posisi dan kecepatan partikel yang sedang bergerak. Untuk
objek berukuran makroskopik, efek ini tidak begitu nyata tetapi, dalam hal
objek mikroskopik seperti elektron, efek ini ternyata sangat signifikan;
artinya, keadaan objek pada saat awal pengamatan akan berbeda dengan
keadaan pada akhir pengamatan.
Untuk memperjelas adanya pengaruh tindakan pengamatan
terhadap objek yang sedang diamati, dapat dipikirkan adanya suatu thought
experiment atau percobaan dalam angan-angan (Gambar 3.4). Oleh karena
percobaan ini tidak pernah dapat dilaksanakan secara fisik (dalam
laboratorium secara visual), maka semua alat hipotetik yang terlibat
dipertimbangkan bekerja secara ideal, 100% efisien, sedangkan hukum-hukum
alam masih tetap dipatuhi. Dalam percobaan ini diandaikan bahwa sebuah
elektron ditembakkan di dalam tabung hampa sempurna dengan kecepatan
tertentu; maka, jejak elektron akan berupa garis lengkung parabola sebagai
akibat gaya gravitasi
bumi (Gambar 3.4a).
Agar elektron dapat terlihat melalui sebuah mikroskop
ideal, maka diperlukan sebuah sumber cahaya yang ideal yang mampu
memancarkan sejumlah foton tertentu dengan energi (frekuensi) atau panjang
gelombang (() tertentu pula. Foton ini harus menumbuk atau berinteraksi
dengan elektron, sebab bila tidak foton hanya lewat saja dan akibatnya
elektron akan nampak transparan/samar. Oleh karena kedua jenis partikel ini
mempunyai massa yang relatif sama, maka elektron akan mengalami rekoil
(pegas-balik) yang signifikan dan kecepatannyapun berubah. Oleh karena itu,
pada interval waktu pengamatan yang sangat kecil berikutnya, elektron akan
terlihat bergerak secara zig-zag sebagai akibat tumbukan-tumbukan foton
berikutnya (Gambar 3.4 b).
Agar gerakan elektron tidak terganggu yang berarti
kecepatan elektron tetap seperti semula, maka energi foton, h(, harus
sekecil mungkin atau panjang gelombang, (, sebesar mungkin. Akan tetapi hal
ini akan berakibat menurunnya daya resolusi mikroskop sehingga posisi
elektron tidak lagi dapat ditentukan secara akurat melainkan berada pada
batas-batas daerah tertentu yang dapat digambarkan sebagai rangkaian
lingkaran-lingkaran kecil pada pengamatan interval waktu tertentu (Gambar
3.4c).
Sebaliknya agar elektron dapat terlihat jelas posisinya

oleh mikroskop, energi foton harus diperbesar, yang berarti ( kecil, tetapi
kecepatan elektron menjadi berubah secara signifikan sebagai akibat
tumbukan dengan foton tersebut sedemikian sehingga kecepatan elektron
menjadi tidak mungkin lagi ditentukan secara tepat. Dengan kata lain, bila
kecepatan elektron akan ditentukan secara teliti, ini berakibat posisi
elektron menjadi kabur, dan sebaliknya bila posisi elektron ingin
ditentukan secara teliti ini berakibat kecepatan elektron menjadi tidak
tentu. Demikian juga pemakaian sumber foton dengan energi medium tentu
masih tetap berpengaruh baik terhadap kecepatan maupun posisi elektron.
Dengan demikian, jejak elektron berubah menjadi pita ketidak-pastian
(Gambar 3.4d) yaitu merupakan produk dari ketidak-pastian kecepatan dengan
ketidak-pastian posisi.
Lebih lanjut Heisenberg dapat menunjukkan bahwa kedua
besaran ketidak-pastian ini tidak pernah lebih kecil daripada harga h / m,
yaitu:
Dx
.
Dv
(
E M
B E D
E q u a t i o n . 3
a t a u
Dx
.
Dp
(
h
. . . . . . . . . . .
( 3 . 3 )
R u m u s a n
t e r s e b u t
m e n u n j u k k a n
b a h w a
m o
m e n t u m
( p )
d a n
p o s i s i
( x )
e l e k t r o n
k e d
u a n y a
t i d a k
d a p a t
d i t e n t u k a n
d e n g a n
t e
p a t
s e c a r a
s e r e n t a k .
P e r l u
d i s a d a r i
b a
h w a
a s a s
k e t i d a k - p a s t i a n ini muncul bukan karena
ketidak-mampuan teknik pengukuran percobaan melainkan karena sifat natural
yang mendasar mengenai pengukuran itu sendiri dan oleh karena itu berlaku
umum. Contoh perhitungan berikut menunjukkan konsekuensi numerik dari asas
ketidak-pastian Heisenberg.
Contoh Perhitungan
(1).
Hitung ketidak-pastian kecepatan elektron bila kita ingin
menentukan posisinya
sedemikian sehingga Dx
=
5 0
p m
( k e m u n g k i n a n
p e n
y i m p a n g a n
p o s i s i )
( 2 ) .
H i t u n g
k e t i d a k - p a s t i a n
p o s i s i
s e b u a h
b o l a
d e n g a n
m a s s a
1 0
g
y a n g
d i l
e m p a r
d e n g a n
k e c e p a t a n
5
m
s - 1
b i l a
k e t e l i t
i a n
k e c e p a t a n n y a
s a m p a i
d e n g a n
s e p e r - s
e r i b u n y a .
( 1 )
Dv
(
E M B E D
E q u a t i o n . 3
(
E
M B E D
E q u a t i o n . 3
(
1 , 4 . 1 0 7
m
s - 1
H a s i l
i n i
j e l a s
m e r u p a k a n
s u a t u
h a r g a
k e t i d a k - p a s t i a n
k e c e p a t a n
y a n g
s i g n i f i
k a n
b e s a r ,
d a n
t i d a k
m u n g k i n
d i a a b a i k
a n
b u k a n !
( 2 )
K e t i d a k - p a s t i a n
k e c e p a t a n
b o l
a
a d a l a h
Dv
=
5 . 1 0 - 3
m
s - 1 ,
m a k
a
Dx
(
E M B E D
E q u a t i o n . 3
(
E M B E D
E q u a t i o n . 3
(
1 , 3 2 3 . 1 0 - 2 9
m
H a s i l
i n i
j e l a s
m e r u p a k a n
h a r g a
k e t i d
a k - p a s t i a n
j a r a k
y a n g
s a n g a t
k e c i l ,
y a
n g
t i d a k
m e m p u n y a i
a p a p u n
s e h i n g g a
d a p a t
d i a b a i k a n
b u k a n !
C o n t o h
p e r h i t u n g a n
d i atas jelas
menunjukkan kesejajaran terhadap sifat gelombang suatu partikel menurut de
Broglie. Dengan demikian, sifat ketidak-pastian ini sangat signifikan untuk
partikel-partikel atomik. Prinsip ketidak-pastian ini jelas bertentangan
dengan asumsi Bohr yang menyatakan bahwa elektron (dalam atom hidrogen)
mempunyai orbit tertentu dengan jari-jari (r) tertentu pula; ini berarti
bahwa ketidak-pastian posisi, Dr ,
a d a l a h
n o l .
M e n u r u t
H e i s e n b e r g ,
a d a l a h
t i d a k
m u n g k i n
u n t u k
m e n g e t a h u i
b a h w a
Dr
=
n o l
t a n p a
m e n g
e t a h u i
k e t i d a k
p a s t i a n
t o t a l n y a .
J a d i ,
j e j a k
e l e k t r o n
t i d a k
l a g i
d a p a t
d i t e n t
u k a n
k e p a s t i a n n y a
s e c a r a
m a t e m a t i k
d a n
s e b a g a i
g a n t i n y a
a d a l a h
b e r u p a
p i t a
k e
t idak-pastian bagi elektron yang bergerak bebas dengan karakteristika
gelombang.
Oleh karena keadaan elektron tidak lagi dapat dilukiskan
secara pasti, maka muncul pendekatan peluang (probabilitas) mendapatkan
elektron yang diasosiasikan dengan fungsi gelombang elektron yang
bersangkutan yang dibahas dalam apa yang disebut sebagai mekanika gelombang
atau kimia kuantum. Oleh karena itu, mempelajari fungsi gelombang elektron
merupakan langkah yang fundamental untuk keperluan elusidasi struktur atom
lebih lanjut. Walaupun materi ini sangat rumit, ada bagian-bagian yang
perlu dikenal saja sebelum sampai pada kesimpulan utama yang mendasar.
3.5
Fungsi Gelombang
Atom hidrogen dan sistem bak-hidrogen (hydrogen-like
system) adalah spesies dengan sebuah elektron; misalnya, He+, dan Li2+,
merupakan sistem yang paling sederhana. Menurut Erwin Schrdinger (1927),
persamaan gelombang stasioner - bebas waktu untuk sistem tersebut
dinyatakan dalam persamaan (3-4), yang cukup rumit penurunanya (tidak kita
bicarakan).
( 2
Y( x , y , z )
+
E M B E D
E q u a t i o n . 3
Y( x , y , z )
=
0
. . . . . . . . .
( 3 . 4 )
d e n g a n
:
Y ( p s i )
=
f u n g s i
g e l o m
b a n g
e l e k t r o n ;
m o
=
m a s s a
e l e k t r o n
d i a
m
( 2
( n a b l a )
(
E M B E D
E q u a t i o n . 3
+
E M B E D
E q u a t i o n . 3
+
E M B E D
E q u a t i o n . 3
=
O p e r a tor Laplace
=
EMBED Equation.3
E = Ek +
V
=
energi total
elektron adalah jumlah energi kinetik, Ek,
dengan
energi potensial, V.
V = - EMBED Equation.3
=
energi
potensial elektron dengan muatan e dan
berjarak
terhadap inti yang mempunyai muatan Z

h = tetapan Planck, dan
x, y,
z = sumbu-sumbu koordinat Cartes.
Ada dua perbedaan pokok teori atom menurut Bohr dengan teori atom mekanika
gelombang yaitu:
(1)
berbeda dengan asumsi Bohr bahwa elektron sebagai partikel
mengorbit dalam
bentuk lingkaran, Schrdinger melukiskan
elektron sebagai gelombang dengan
jejak menurut persamaan
gelombang (3.4) tersebut, dan
(2)
demikian juga dengan asumsi Bohr bahwa momentum sudut
elektron dalam
orbitnya bersifat kuantum (mvr = nh /2 p) ,
s e b a l
i k n y a
S c h r d i n g e r
m e n g i d e n t i f i k a s i
f r e k u e n s i
s i f a t
g e l o
m b a n g
e l e k t r o n
d e n g a n
e n e r g i
y a n g
m e m e n u h i
m e n g a n
z ) ,
d a
a m
b e n
f e r i s d e n g a n
0o
n g e n a i
k o o r d i
5
y a n g
y a i t u :
z
=
r
=
r
s i
2
.
d
p
t
b
u
a
u
o
h
p
t
n a
m
n
t
k
l
a
,
r
t
e
a s u m s i
P e r s a m a
g
k o o r d
l e b i h
p e r s a m
a
a t a u
r g a - h a r
d a n
a n s f o r m
i n i
d i
m b e r i k a
E i n s t e i n ,
a n
( 3 . 4 )
t
i n a t
C a r t e
m u d a h
d i s e
a a n
d e n g a n
k u t u b - p o l a
g a
r
=
0
=
0 o 2 p.
a s i
a n t a r a
p e r o l e h
d a
n
e m p a t
r u
E
e r s e
s
( x
l e s a
k o o
r
( r
(
I n f o
k e d
r i
G
m u s a
=
b u
,
i k
r d
,
,
r m
u a
a m
n
h n.
t
y a n
y ,
d a
a n
d a
i n a t
q,
)
q =
a s i
m
m a c a
b a r
3
p o k o k
g
n
l
s
e
m
.
c o s
q ;
x
=
r
s i n q c o s
;
y
n q s i n ;
d a n
r 2
=
x 2
+
y 2
+
z
. .
. . . . .
( 3 . 5 )
p e r s a m a a n
( 3 . 4 )
s e t e l a h
d i t r a n s f o r m a s i
k e
d a l a m
k o o r d i
n a t
b o l a
d a p a t
d i t u l i s k a n
s e c a r a
u m u m
s e b a g a i :
Y( r , q, f)
=
R
( r )
.
Q ( q)
.
F ( )
. . . . . . . . . . . . . . . . .
( 3 . 6 )
P e r s a m a a n
( 3 . 6 )
p
r o d u k
d a r i
t i g a
m a c a m
f u n g s i
( R ,
Q,
d a
n
F)
d e n g a n
t i g a
m a c a m
v a r i a b e l
s e c a r a
b e r u r u t a n
( r ) , ( q)
d a n
( )
y a n g
t e r s u s
u n
s e c a r a
t e r p i s a h .
P e m e r i k s a a n
l e b i h
l a n j u t
a d a n y a
b e s a r a n - b e s a
r a n
t e r t e n t u
y a n g
m e n g o n t r o l
h a r g a
m a s
i n g - m a s i n g ,
f u n g s i
R a d i a l j a r a k ,
R
( r
) ,
f u n g s i
s u d u t ,
Q ( q )
d a n
F ( ) ;
b e s
a r a n - b e s a r a n
i n i
a d a l a h
n ,
!,
d a n
m ,
y
a n g
k e m u d i a n
d i s e b u t
s e b a g a i
b i l a n g a n
k u a n t u m
y a n g
t e r n y a t a
m u n c u l
s e c a r a
m a
t e m a t i s
a l a m i a h
s e b a g a i
k o n sekuensi
penyelesaian persamaan fungsi gelombang (3.4). Oleh karena itu, persamaan
(3.6) menjadi lebih informatif bila dituliskan dalam bentuk persamaan (3.7)
yang mengandung variabel n,
EMBED "Equation" \* mergeformat
, dan m
sebagai bilangan kuantum yang mengontrol harga-harga masing-masing fungsi
sebagai berikut:
Yn ,
E M B E D
" E q u a t i o n "
\ *
m e r g e f o r m a t
, m (r , q, )
=
R n ,
E M B E D
" E q u a t i o n "
\ *
( r )
.
Q
E M B E D
" E q u a t i o n "
\ *
,m
(q ) .
Fm ( )
. . . . . . . . . . . . . .
( 3 . 7 )
D e n g a n
d e m i k i a n ,
f u n g s i
g e l o m
b a n g
e l e k t r o n
d a p a t
d i f o r m u l a s i k a n
s e b
a g a i
p r o d u k
t i g a
f u n g s i
g e l o m b a n g ,
m a s
i n g - m a s i n g
t e r d i r i
a t a s
s a t u
v a r i a b e l
y a n g
b e r b e d a
s a t u
d e n g a n
y a n g
l a i n
y a i
t u :
( 1 )
f u n g s i
g e l o m b a n g
R a d i a l ,
Y( r
)
=
R n ,
E M B E D
" E q u a t i o n "
\ *
m e r g e f o r
m a t
( r )
,
y a n g
b e r g a n t u n g
p a d a
v a r i a
b e l
r
y a i t u
j a r a k
e l e k t r o n
( t i t i k
P )
t e r h a d
a p
i n t i
a t o m
s e b a g a i
t i t i k
p u s a t
s u m b u
;
f u n g s i
i n i
h a r g a n y a
d i t e n t u k a n
o l e h
b i l a n g a n
k u a n t u m
n
d a n
E M B E D
" E q u a t i o
n "
\ *
.
( 2 )
f u n g s i
g e l o m b a n g
s u d u t ,
Y( q)
=
Q
E M B E D
" E q u a t i o n "
\ *
,
m ( q)
,
y a n g
b e r g a n t u n g
p a d a
v a r i a b e
l
s u d u t
q;
f u n g s i
i n i
h a r g a n y a
d
i t e n t u k a n
o l e h
b i l a n g a n
k u a n t u m
E M B E D
" E q u a t i o n "
\ *
d a n
m .
( 3 )
f u n g s i
g e l o m b a n g
s u d u t
Y( )
=
Fm
( ) ,
y a n g
b e r g a n t u n g
p a d a
v a r i a b e l
s u
d u t
; f u n g s i
i n i
h a r g a n y a
d i t e n t u k a n
h a n y a
o l e h
bilangan kuantum m.
Detil transformasi kedalam koordinat kutub agar diperoleh
bentuk umum persamaan 3.7, dan penyelesaiannya secara terpisah adalah
masalah matematik dan sangat rumit, dan ini jelas diluar bidang pembicaraan
ini. Namun, agar tidak menimbulkan miskonsepsi, hasil akhir perlu
ditampilkan dan dipahami lebih lanjut yakni sebagai berikut:
Yn ,
E M B E D
" E q u a t i o n "
\ *
m e r g e f o r m a
t
, m (r , q,f) =
E M B E D
E q u a t i o n . 3
. . . . . . . . . . . . . .
( 3 . 8 )
H a s i l
p e n y e l e s a i a n
m a t e m a t i s
t e r s e b u t
s a n g a t
r u m i t
b u k a n ?
N a m u n ,
j i
k a
k i t a
t e l i t i
l e b i h
c e r m a t
k i t a
a k a n
t e m u k a n
e s e n s i
y a n g
h a r u s kita ketahui yakni bahwa
hasil ini hanya ditentukan oleh faktorial (n- EMBED "Equation" \*
mergeformat
-1)!, dan ( EMBED "Equation" \* mergeformat
|m|)!
Ingatkah Anda informasi yang telah kita terima di SMA, bahwa faktorial
tidak boleh berharga negatif dan pecahan? Faktorial inilah yang memberikan
pembatasan-pembatasan terhadap harga-harga n,
EMBED "Equation" \*
mergeformat
, m (tepatnya m !) ,
d a n
k o m b i n a s i n y a
y a
k n i
b a h w a :
( a ) .
n
d a n
E M B E D
" E q u a t i o n "
\ *
m e
r g e f o r m a t
m e r u p a k a n
b i l a n g a n
d i s k r e t
,
p o s i t i f
b u l a t
i n t e g e r
1 ;
h a r g a - h a r g
a
i n i
a d a l a h ,
n
(
(
E M B E D
" E q u a t i o n "
\ *
+
1 ) ,
E M B E D
" E q u a t i o
n "
\ *
(
0
,
d a n
m
=
!;
j a d i ,
n
=
1 ,
2 ,
3 ,
4 ,
5 ,
& & & .
";
E M B E D
" E q u a t i o n "
\ *
=
0 ,
1 ,
2 ,
3 ,
4 ,
5 ,
& & . .
( n - 1 ) ;
m
=
0 ,
1 ,
2 ;
3
& . . ;
( b ) .
t a m b a h a n
p u l a ,
a d a
h u b u n g a n
y a n g
u n i k
a n t a r
n i l a i
k e t i g a n y a
y a n g
d i m u n
g k i n k a n ,
d a n
k o m b i n a s i
h a r g a - h a r g a
y a n
g
d i i j i n k a n
u n t u k
n
=
1
4
a d a l a h
s e b
a g a i
b e r i k u t :
n
1
2
3
4
! 0
0
1
0
1
2
0
1
2
3
m
a t
a u
m ! 0
0
0 ;
1
0
0 ;
1
0 ;
1 ;
2
0
0 ;
1
0 ;
1 ;
2
0 ;
1 ;
2 ;
3
N a h
,
h u b u n g a n
n u m e r i k
k e t i g a
b i l a n g a n
k u a
n t u m
n ,
E M B E D
" E q u a t i o n "
\ *
m e r g e f o r m
a t
,
d a n m dengan koordinat Cartes, yang dengannya notasi orbital
sering dinyatakan, dapat diperiksa pada Tabel 3.4, dan rincian penyelesaian
fungsi gelombang polar bersama dengan koordinat Cartes ditunjukkan pada
Tabel 3.5.
Tabel 3.4
Kombinasi harga-harga n , EMBED "Equation" \*
mergeformat
, dan m EMBED "Equation" \* mergeformat
, yang diijinkan
n
(ada n macam ) m atau m EMBED
"Equation" \* mergeformat
, ada (2 EMBED "Equation" \* mergeformat
+
1) mac a m ,
d a n
n o t a s i
o r b i t a l
d a l a m
s u m b u
C a r t e s
H a r g a
N o t a s i
0
1
2
3
1
0
s
1 s
2
0
s
2 s
1
p
2 p z
2 p x
,
2 p y
3
0
s
3 s
1
p
3
p z
3 p x
,
3 p y
2
d
3 d z 2
3 d x z
,
3 d y z
3 d x y
,
3 d x 2 y 2
4
0
s
4 s
1
p
4 p
z
4 p x
,
4 p y
2
d
4 d z 2
4 d x z
,
4 d y z
4
d xy , 4dx2- y2
3 f* 4fz3 4fxz2, 4fyz2 4fz(x2-y2) , 4fzxy 4fx(x2-3y2) ,
4fy(3x2-y2)
f** 4fz3 4fx3 , 4fy3 4fz(x2-y2) , 4fzxy 4fx(z2-y2) , 4fy(z2x2) Catatan: Orbital f mempunyai 2 bentuk yakni bentuk umum - general set
(f*) dan bentuk kubik - cubic set (f**); keduanya memiliki 3 label orbital
yang sama sedangkan 4 yang lain berbeda. Bentuk umum lebih bermakna untuk
geometri selain kubus misalnya trigonal planar dan tetragonal, sedangkan
bentuk kubus lebih bermakna untuk geometri kubus yakni tetrahedron dan
oktahedron. Seperti halnya orbital dz2 adalah bentuk singkat dari d2z2- x2y2 atau d3z2- r2, demikian juga: fz3 = fz(5z2-3r2) ; fx3 = fx(5x2-3r2) ;
fy3 = fy(5y2-3r2) ; sedangkan fxz2 = fx(5z2-3r2), dan 4fyz2 = fy(5z2-3r2).
Mengapa keempat formula orbital f yang lain hasil cubic-set berbeda dari
hasil general-set? Perbedaan ini secara matematis valid semuanya sesuai
lingkungan geometrinya, sebab keempat formula orbital f cubic-set
sesungguhnya hanyalah hasil kombinasi 2 set orbital dari hasil general-set.
Jadi, fx3 = -[ EMBED Equation.3
fxz2 - EMBED Equation.3
fx(x2-3y2)];
fy3 = -[ EMBED Equation.3
fyz2 - EMBED Equation.3
fy(3x2-y2)];
fx(z2-y2) = [ EMBED Equation.3
fxz2 - EMBED Equation.3
fx(x23y2)];dan fy(z2-x2) = [ EMBED Equation.3
fyz2 - EMBED Equation.3
fy(3x2-y2)].
Nah, lalu kebenaran apa yang dapat Anda petik dari Tabel
3.4 tersebut? Ada hubungan yang pasti antara nilai m EMBED "Equation" \*
mergeformat
dengan lambang-formula orbital, misalnya untuk
EMBED
=1, m EMBED "Equation" \* mergeformat
=
0 selalu menunjuk orbital pz. Banyak dijumpai buku teks, guru maupun
(maha)siswa menunjukkan miskonsepsi dengan secara sembarangan mengurutkan
abjad px, py, pz sesuai dengan urutan nilai m EMBED "Equation" \*
mergeformat
= -1, 0, +1 atau m EMBED "Equation" \* mergeformat
=
+1, 0, -1; bahkan ada yang berpendapat bahwa tidak mungkin ditentukan
hubungan antara nilai numerik m EMBED "Equation" \* mergeformat
d e
n g a n
l a b e l
f o r m u l a
o r b i t a l
p
( d a n
j u g a
d ) .
3 . 6
I n t e r p r e t a s i
f u n g s i
g e l o m b a n g
F u n g s i
g e l o m b a n g ,
Y,
s e s u n g g u
h n y a
t i d a k
m e m p u n y a i
a r t i
f i s i k
y a n g
b
e r m a k n a ,
m e l a i n k a n
a s p e k
m a t e m a t i s
t e r
u t a m a
y a n g
b e r k e n a a n
d e n g a n
s i f a t
s i m e
t r i .
N a m u n ,
a s p e k
k i m i a w i
y a n g
f u n d a m e
n t a l
a d a l a h
b e s a r a n
k u a d r a t
f u n g s i
g e l
o m b a n g
e l e k t r o n
i t u
s e n d i r i
y a n g
p r o p o
r s i o n a l
d e n g a n
i n t e n s i t a s
e l e k t r o n .
J a
d i ,
+"Y2 d V
a t a u
+"Y. Y*d V
d i p a h a m i
s e b a g a
i
u k u r a n
p e l u a n g
d a r i
k e b e r a d a a n
s u a t u
e l e k t r o n
p a d a
d a e r a h
d V
( d e f e r e n s i a l
v
o l u m e ) .
I s t i l ah lain yang sering digunakan untuk menunjuk pada
peluang (probabilitas) dari keberadaan elektron di sepanjang waktunya di
seputar inti atom adalah rapatan elektron atau awan elektron, dan inilah
yang dapat diukur atau diamati melalui percobaan difraksi sinar-X.
Nah, lalu apa yang dimaksud dengan orbital itu? Istilah
orbital atom sesungguhnya menunjuk pada fungsi gelombang total, Yn ,
E M
B E D
" E q u a t i o n "
\ *
, m (r ,
q, ),
n a m u n
k a r e n a
v i s u a l i s a s i
f u n g s i
i n i
s e c a r a
u t u h
s a n g a t
m e l e l a h k a n
m a k a
s e r i n g
f u n g s i
i n i
d i l u k i s k a n
s e c a r a
t e
r p i s a h
y a i t u
s e b a g a i
f u n g s i
r a d i a l ,
Yn
,
E M B E D
" E q u a t i o n "
\ *
( r )
y a n g
b e r u r u s a n
d e n g a n
j a r a k
( e l e k t r o n )
t e r h a d a p
i n t i ,
d a n
f u n g s i
s u d u t
( p o l a r
)
t o t a l ,
Y
E M B E D
" E q u a t i o n "
\ *
m e r g e f
o r m a t
, m (q, ), y a n g
b e r u r u s a n
d e n g a n
o r i e n t a s i
e l e k t r o n
d a l a m
r u a n g
d i
s e p u
t a r
i n t i .
O l e h
k a r e n a
d a l a m
b a n y a k
a s p
e k
f u n g s i
s u d u t
l e b i h
b e r m a k n a
p a d a
o r
i e n t a s i
e l e k t r o n ,
m a k a
o r b i t a l
a t o m
s e
r i n g
m e n u n j u k
p a d a
f u n g s i
i n i ;
b e g i t u
j u g a
k u a d r a t
a m p l i t u d o n y a .
G r a f i k
a t a u
g a m b a r
y a n g
p a l i n
g
s e r i n g
d i j u m p a i
p a d a
b e r b a g a i
b u k u
t
e k s
b i a s a n y a
m e n u n j u k
p a d a
Yn ,
E M B E D
"
E q u a t i o n "
\ *
( r ) ,
Y2 n ,
E M
B E D
" E q u a t i o n "
\ *
( r ) ,
Y
E M B E D
" E q u a t i o n "
\ *
, m
(q, ),
d a n
Y2
E M B E D
" E q u a t i o n "
\ *
m e r
g e f o r m a t
, m (q, );
s a n g a t
j a r a n g
d i t e
m u i
b e n t u k
t o t a l n y a
s e b a g a i
d i a g r a m
k o
n
g
h
a
t
a
y
n
m
t
e
a
s
o
l
a
i
u
f
r
i
m
r
o
u
k
,
d
n g
h
y a
d a r i
Y2 n ,
E M B E D
" E q u a t i o n "
\ *
m e r
r m a t
, m (r , q, ). O l e h
k a r e n a
i t u
s
b e r h a t i - h a t i
d a l a m
m e n g i n t e r p r e t
a n
a r t i
d a n
b e n t u k
s u a t u
o r b i t a l
a
d a n
l e b i h
t e p a t
b i l a
n o t a s i
o r b i t
i l e n g k a p i
d e n g a n
f u n g s i
g e l o m b a n g
b e r s a n g k u t a n .
D a l a m
k e s e m p a t a n
i
a n y a
d i b a h a s
p e m a h a m a n
o r b i t a l
a t o
ng menggambarkan bagian sudutnya saja.
Dengan menggunakan keempat sifat pokok pada sistem
koordinat tersebut, harga m atau m EMBED "Equation" \* mergeformat
dapat diturunkan langsung ke sumbu-sumbu koordinat Cartes dan selanjutnya
dituliskan sebagai subskrip suatu notasi orbital dengan menghilangkan
pembagi, r.
Sebagai contoh, untuk
=1,
terdapat tiga macam harga m EMBED "Equation" \* mergeformat
yaitu -1,
0, dan +1. Berdasarkan perjanjian sistem koordin a t
G a m b a r
3 .
5 ,
m a k a
m
E M B E D
" E q u a t i o n "
\ *
m e r g e f o r
m a t
=
0
m e r u p a k a n
f u n g s i
g e l o m b a n g
y a n g
d i t u r u n k a n
d i
s e p a n j a n g
s u m b u
z ,
d a n
m
E M B E D
" E q u a t i o n "
\ *
=
1
d i
s e p a n j a n g
s u m b u
x
d a n
y ,
s e
h i n g g a
n o t a s i
o r b i t a l
i n i
a d a l a h :
Y1
=
F u n g s i
r b i t a l
T a b e l
3
k a r e n a
n y a ,
w a
i k e t a h u
a l a m
k e
3 . 7
B e
a t o m
o
a
b
a
S
o
(
a
t
3
l
n
e
l
e
r
a r
h a
n t u
y a
b a g
b i t
( T a
( (
k a n
. 6 ) .
(
r
k
n
a
a
b
=
n
=
p x
,
g e l o m b a n g
s ,
p ,
d ,
d
. 5 .
O r b i
s a n g a t
s u k
l a u p u n
s e c
i
p e r s a m a a
s e m p a t a n
i
n t u k
d a n
s
T a b
g a d a
g
b
i
c
l
p
e l .
0 i l a
A
e
h
n
e
o
z
t a s
l
3 .
a r g a
s i f
r s a n
n t o h
y a n
3 . 5 )
1 8 0 0 )
i
c o s
d a s
5 ) ,
s u
a t
g k u
p a
g
t
.
D
,
m
(
p z
,
d a n
p y
b a g i a n
p o l a r
a n
f
d i t u n j u k
t a l - o r b i t a l
y
a r
d i g a m b a r k a
a r a
m a t e m a t i s
n n y a ,
t i d a k
d
n i .
i f a t
s i m e t r i
a r
m
d u
s i
t a
l i
i d
e n
a k
m a
a
t
m
n
n
a
g
a
u
f u n g
k a
d
q
e t r i
d a p
g
s e
k
l a
a n
m
k i t
p u n
s i
g
e n g a
d a n
o r b
a t
d
d e r h
i n
a
e m a s
a
a k
c o s 2
Y1 ,
u n t u k
o
k a n
p a d a
a n g
l a i n
n
b e n t u k
s u d a h
d
i b a h a s
d
o r b i t a l
e l o m b
n
m e m
a t a u
i t a l i l u k i
a n a
a
d a l a h
u k k a n
a n
m e
(
( T
a n g
a s u
o r b
s k a
d a l
c o
a n
n d a
a b e
p
k k
,
i t
n .
a h
s
g k
p a
l
L a l u
j i k a
j i k a
d a t a
T a b e l
3 . 6
k i t a
l u k i s k a n
p a da kertas grafik polar (polar-graph) dua
dimensi, hasilnya sebagaimana ditunjukkan Gambar 3.6. Nah, Anda tentu sudah
sangat familiar dengan gambar orbital pz bukan? Secara sama semua fungsi
gelombang Tabel 3.5 dapat dilukiskan, dan secara kualitatif ditunjukkan
pada Gambar 3.7 dan 3.8.
Tabel 3.6
Beberapa nilai cos
d a n
c o s 2
0
1 5
3 0
4 5
6 0
7 5
9 0
c o s
1
0 , 9 6 6
0 , 8 6 6
0 , 7 0 7
0 , 5
0 , 2 5 9
0
c o s 2
1
0 , 9 3
3
0 , 7 5 0
0 , 5
0 , 2 5
0 , 0 6 7
0
1 0 5
1 2 0
1 3 5
1 5 0
1 6 5
1 8 0
& & .
c o s
- 0 , 2 5 9
- 0 , 5
- 0 , 7 0 7
- 0 , 8 6 6
- 0 , 9 6 6
- 1
& & . .
c o s 2
0
, 0 6 7
0 , 2 5
0 , 5
0 , 7 5 0
0 , 9 3 3
1
& &
E M B E D
W o r d . P i c t ure.8
EMBED
Word.Picture.8
EMBED
Word.Picture.8
Gambar 3.7
Bentuk (irisan) dan sifat simetri orbital s, p,
dan d
Orbital
Orbital 1s mempunyai fungsi gelombang yang berharga

konstan, ( EMBED Equation.3
), tidak bergantung pada sudut
q
m a u
p u n
;
o l e h
k a r e n a
i t u ,
i a
b e r b e n t u k
b o l a - b u l a t
s i m e t r i
d e n g a n
t a n d a
p o s i t i
f
d i
s e g a l a
a r a h .
I s t i l a h
s i m e t r i
d i p
a k a i
u n t u k
m e l u k i s k a n
k e s a m a a n
a n t a r a
d u a
t i t i k
a t a u
d a e r a h
y a n g
t e r l e t a k
p a
d a
g a r i s
l u r u s
d a n
s a l i n g
b e r s e b e r a n g a
n
d e n g a n
t i t i k
p u s a t
s imetri (0,0,0).
Orbital p , d, dan f
Orbital-orbital p, d, dan f, pada dasarnya berbentuk
cuping-dumbbell bagai balon terpilin), yang mempunyai orientasi sesuai
dengan fungsi gelombang bagian polar yang bersangkutan. Orbital px, py, dan
pz secara berturut-turut, masing-masing cuping terletak di sepanjang sumbu
x, y, dan z. Dengan mudah dapat ditentukan bahwa cuping di sepanjang sumbu
positif bertanda positif (+) dan sebaliknya di sepanjang sumbu negatif
bertanda negatif (-). Terhadap titik pusat simetri (0,0,0), dikatakan bahwa
orbital p bersifat antisimetri, karena kearah yang berlawanan dengan jarak
yang sama pada garis lurus yang melalui titik pusat simetri didapatkan
titik-titik atau daerah-daerah yang sama namun berlawanan tanda.
Orbital-orbital d terbagi dalam dua kelompok yaitu (1) dz2
dan dx2-y2, yang mempunyai cuping-cuping yang terletak di sepanjang sumbusumbu Cartes, dan (2) dxy, dxz, dan dyz, yang mempunyai cuping-cuping yang
terletak di antara setiap dua sumbu Cartes. Sifat simetri orbital d dengan
mudah dapat ditentukan sebagai berikut.
Orbital dz2 sesungguhnya singkatan dari d(2z2-x2-y2), maka sebagai akibat
produk
kuadrat masing-masing sumbu, cuping di sepanjang sumbu z bertanda
positif dan sebaliknya ring-donut yang membelah bidang xy bertanda negatif.
Secara sama dapat ditentukan bahwa untuk orbital dx2-y2, cuping pada
sepanjang sumbu x bertanda positif dan pada sepanjang sumbu y bertanda
negatif.
Untuk orbital dxy , dxz , dan dyz , tanda setiap cuping ditentukan oleh
produk dari
dua sumbu Cartes yang mengapitnya. Sebagai contoh, setiap cuping yang
terletak antara sumbu x+ dan y+, dan antara sumbu x- dan y-, keduanya
bertanda positif; sedangkan cuping-cuping yang terletak antara sumbu-sumbu
x+ dan y-, antara x- dan y+, keduanya bertanda negatif. Dengan demikian,
orbital d bersifat simetri.
EMBED
Word.Picture.8
Gambar 3.8
Bentuk
dan sifat simetri orbital f (model cubic set); orbital fx3 dan
fy3 mempunyai bentuk
yang serupa dengan orbital fz3 dengan cuping
masing-masing terletak di sepanjang sumbu x dan
y.
Orbital f dalam medan kubus dapat dikelompokkan menjadi
tiga kelompok yaitu (1) fxyz, (2) fx(z2-y2), fy(z2-x2), fz(x2-y2), dan (3)
fx3, fy3, fz3; kelompok (1) dan (2) terdiri atas delapan cuping dan
kelompok (3) mirip orbital dz2 namun dengan dua ring-donut.
Penentuan
tanda positif-negatif pada setiap cuping sedikit lebih kompleks, namun pada
das a r n y a
s a m a
d e n g a n
c a r a
y a n g
t e r d a h u l
u
y a i t u
m e r u p a k a n
p r o d u k
d a r i
s u m b u - s u
m b u
C a r t e s
y a n g
m e n g a p i t n y a .
( T a n d a
p o
s i t i f - n e g a t i f
b a g i
s e t i a p
c u p i n g
d a p a t
p u l a
d i t e n t u k a n
d e n g a n
m e m a s u k k a n
h a r g
a - h a r g a
q d a n
b a g i
s e t i a p
p o s i s i
c u p
i n g
m e n u r u t
p e r s a m a a n
f u n g s i gelombang polar
dari orbital yang bersangkutan).
Untuk orbital fxyz, cuping yang diapit oleh tiga sumbu positif x+- y+z+, bertanda
positif, demikian juga cuping yang diapit oleh dua sumbu negatif dan satu
sumbu positif; sedangkan cuping yang diapit oleh tiga sumbu negatif
bertanda negatif, demikian juga cuping yang diapit dua sumbu positif dan
satu sumbu negatif.
(2)
Untuk orbital kelompok kedua, misalnya fx(z2- y2), sumbu x
menghasilkan dua
macam daerah positif dan negatif, tetapi semua daerah sepanjang sumbu z
bertanda positif dan semua daerah sepanjang sumbu y bertanda negatif
sebagai akibat produk kuadratnya. Oleh karena itu, cuping-cuping yang
diapit oleh sumbu x+ dengan sumbu y keduanya bertanda negatif, tetapi bagi
kedua cuping yang diapit oleh sumbu x- dengan sumbu y bertanda positif.
Demikian seterusnya cuping-cuping yang lain dapat dikenali tandanya, dan
dengan cara yang sama dapat diidentifikasi cuping-cuping orbital fy(z2-x2)
yang terdiri atas sumbu-sumbu y+, y-, z+, dan x-, dan orbital fz(x2-y2)
yang terdiri atas sumbu-sumbu z+, z-, x+, dan y-.
(3)
Orbital-orbital fx3 , fy3 , dan fz3 dapat diidentifikasi
tandanya seperti halnya pada
orbital p (karena produk pangkat satu mempunyai tanda yang sama dengan
produk pangkat tiga). Ring pada daerah sumbu positif bertanda negatif,
demikian pula sebaliknya sebagai akibat produk dari - r2 dengan salah satu
sumbunya; hal ini dapat pula diturunkan dari bentuk rumusan orbital yang
sesungguhnya, misalnya orbital fz3 adalah singkatan dari orbital fz(5z23r2) atau fz(2z2 - 3x2 -3y2) (Tabel 3.5).
Jadi, orbital f bersifat antisimetri. Istilah lain yang
dipakai untuk melukiskan sifat kesimetrian suatu orbital adalah sifat
gerade (bahasa Jerman) disingkat g yang artinya even atau genap bagi
orbital yang bersifat simetri, dan un-gerade disingkat u yang artinya odd
atau gasal bagi orbital yang bersifat antisimetri. Ada hubungan antara
harga bilangan kuantum sekunder, EMBED "Equation" \* mergeformat
,
dengan sifat kesimetrian orbital yang bersangkutan yaitu bersifat g untuk
berharga genap, dan bersifat u untuk
berharga gasal. Jadi, orbital s
( EMBED "Equation" \* mergeformat
= 0) dan d ( EMBED "Equation" \*
mergeformat
= 2) bersifat simetri atau gerade, g, dan orbital p
( EMBED "Equation" \* mergeformat
= 1) dan f ( EMBED "Equation" \*
mergeformat
= 3) bersifat antisimetri atau un-gerade, u.
Tabel 3.7
Fungsi gelombang polar untuk orbital s, p, d, dan f
yang
diturunkan dari
atom bak-hidrogen (hydrogen-like atom)
Notasi
faktor normalisasi 1 (satu) (b) Orbital
mergeformat
Bentuk sudut Bentuk Cartes
(a) Fungsi gelombang dengan

m EMBED "Equation" \*
s 0
0
(1/4 p)
p z
1
0
( 3 / 4 p)
c o s
q ( 3 / 4 p)
(
E M B E D
E q u a t i o n . 3
)
p
x
1
1
( 3 / 4 p)
s i n
q c o s
( 3 / 4 p)
(
E M B E D
E q u a t i o n . 3
)
p y
1
1
( 3 / 4 p)
s i n
q
s i n
( 3 / 4 p)
(
E M B E D
E q u a t i o
n . 3
)
d z 2
( c )
2
0
( 5 / 1 6 p)
( 3
c o s
2
q 1
)
( 5 / 1 6 p)
(
E M B E D
E q u a t i o n . 3
)
d x z
2
1
( 1 5 / 4 p)
s i n
q c o s
c o s
q ( 1 5 / 4 p)
(
E M B E D
E q u a t i o n . 3
)
d y z
2
1
( 1 5 / 4 p)
s i n
q
s i n
c o s
q
( 1 5 / 4 p)
(
E M B E D
E q u a t i o n . 3
)
d x 2 - y 2
2
2
( 1 5 / 1 6 p)
s i n 2
q
c o s
2
( 1 5 / 1
6 p)
(
E M B E D
E q u a t i o n . 3
)
d x y
2
2
(
1 5 / 1 6 p)
s i n 2
q
s i n
2
( 1 5 / 1 6 p)
(
E M B E D
E q u a t i o n . 3
)
f z 3
( d )
3
0
( 7
/ 1 6 p)
( 5
c o s 3
q
3
c o s
q)
( 7 / 1 6 p)
(
E M B E D
E q u a t i o n . 3
)
f x 3
3
1
( 1 0
5 / 1 6 p)
s i n
q c o s
f
( c o s 2
q - s i n 2
q
s i n 2
)
( 1 0 5 / 1 6 p)
(
E M B E D
E q u a t i o
n . 3
)
f y 3
3
1
( 1 0 5 / 1 6 p)
s i n
q s
i n
( c o s 2
q - s i n 2
q
c o s 2
)
( 1 0 5 / 1 6 p)
(
E M B E D
E q u a t i o
n . 3
)
f z ( x 2 - y 2 )
3
2
( 1 0 5 / 1 6 p)
c o s
q
s i n 2
q c o s
2 ( 1 0 5 / 1 6 p)
(
E M B E D
E q u a t i o n . 3
)
f x y z
3
2
( 1 0 5 / 1 6 p)
s
i n 2
q c o s
q
s i n
2 ( 1 0 5 / 1 6 p)
(
E M
B E D
E q u a t i o n . 3
)
f x ( z 2 - y 2 )
3
3
( 7 / 1
6 p)
s i n
q c o s
( 5
s i n 2
q c o s 2
3 )
( 7 / 1 6 p)
(
E M B E D
E q u a t i o n . 3
)
f y (
z 2 - x 2 )
3
3
( 7 / 1 6 p)
s i n
q s i n

( 5
s i n 2
q s i n 2
-
3 ) ( 7 / 1 6 p)
(
E M B E D
E q u a t i o n . 3
)
C a
t a t a n :
( a )
N i l a i
p o s i t i f
d a n
n e g a t i f
b i l a n
g a n
k u a n t u m
m
E M B E D
" E q u a t i o n "
\ *
m e r g
e f o r m a t
m a s i n g - m a s i n g
m e n u n j u k
p a d a
c o s
m
( a t a u
s u m b u
x )
d a n
s i n
m
( a t a u
s u m b u
y )
( b )
U n t u k
m e m b a n d i n g k a n
f u n g s i
g e l o
m b a n g
y a n g
s a t u
t e r h a d a p
y a n g
l a i n
d i p
e r l u k a n
f a k t o r
n o r m a l i s a s i
s e d e m i k i a n
s e h i n g g a :
E M B
E D
E q u a t i o n . 3
Y*Y d v
=
f a k t o r
n o r m a l i
s a s i ,
d i m a n a
d v
=
r 2
s i n
q d q d d r
a d a l a h
d i f e r e n s i a l
v o l u m e ,
d a n
i n t e g r a
l
d i a m b i l
p a d a
s e m u a
r u a n g ;
Y* m e r u p a k
a n
k o m p l e k s
k o n y u g a s i
d a r i
Y d a n
s e r i n
g
Y*=
Y s e h i n g g a
Y*. Y =
Y2.
P a u l i n g
m e
n g a m b i l
h a r g a
f a k t o r
n o r m a l i s a s i
s a t
u
( 1 )
u n t u k
f u n g s i
g e l o m b a n g
s e c a r a
k
e s e l u r u h a n ,
s e d a n g k a n
E i n s t e i n
m e n g a m
b i l
h a r g a
4 p
u n t u k
f u n g s i
g e l o m b a n g
p o l a r
s a j a .
( c )
O r b i t a l
d z 2
m e r u
p a k a n
s i n g k a t a n
d a r i
o r b i t a l d(3z2 - r2) atau
d(2z2 - x2 - y2) yang tidak lain merupakan hasil kombinasi linear
penjumlahan dari orbital d(z2 - y2) dan orbital d(z2 -x2).
(d)
Orbital f mempunyai dua macam fungsi gelombang yaitu fungsi
gelombang umum (general set)
dan fungsi gelombang kubus (cubic set); dalam tabel ini adalah
fungsi gelombang cubic set.
3.8
Bilangan kuantum
Sebegitu jauh postulat tentang bilangan kuantum utama, n,
oleh Bohr dan bilangan kuantum azimut,
EMBED "Equation" \*
mergeformat
, oleh Sommerfeld telah berhasil dibuktikan secara meyakinkan
melalui persamaan Schrdinger menurut teori mekanika gelombang, dan bahkan
juga bilangan kuantum magnetik, m atau tepatnya m EMBED "Equation" \*
mergeformat
. Ketiga bilangan kuantum ini dengan demikian muncul secara
natural - matematis.
Bilangan kuantum utama, n, yang mempunyai nilai 1, 2,
3, ..... , n, menyatakan ukuran volume atau jari-jari atom dan tingkattingkat energi kulit utama. Terjadinya garis-garis spektrum deret Lyman,
Balmer, Paschen, Brackett, dan Pfund dalam spektrum hidrogen
diinterpretasikan sebagai akibat terjadinya transisi elektronik dari n
yang lebih tinggi ke n yang lebih rendah.
Bilangan kuantum azimut,
, yang mempunyai nilai 0, 1, 2, 3, .......... , (n-1), menunjuk pada
adanya sub-kulit (orbital) dan bentuknya. Munculnya garis-garis plural
yang sangat berdekatan dari spektrum yang semula nampak sebagai garis
tunggal, mempersyaratkan adanya sub-sub kulit atau beberapa orbital pada
tiap kulit utama n. Garis-garis plural ini diinterpretasikan sebagai
akibat terjadinya transisi elektronik dari sub-sub kulit dalam n yang
lebih tinggi ke kulit atau sub-sub kulit dalam n yang lebih rendah.
Bilangan kuantum magnetik, m atau m EMBED "Equation" \*
mergeformat
, yang mempunyai nilai 0, 1 ,
2 ,
. . . . . ,

E M B E D
" E q u a t i o n "
\ *
m e n u n j u k
p a d a
o r i e n t a s i
a t a u
a r a h
o r b i
t a l .
G e j a l a
e f e k
Z e e m a n
y a n g
s e m u l a
t i
d a k
d a p a t
d i j e l a s k a n
o l e h
B o h r
m a u p u n
S o m m e r f e l d
d a p a t
d i j e l a s k a n
d e n g a n
m e n
g i n t r o d u k s i k a n
b i l a n g a n
k u a n t u m
i n i .
J
a u h
s e b e lum Bohr mengemukakan teori atomnya, Zeeman pada tahun 1896
mengamati adanya pemisahan (splitting) garis spektrum tunggal menjadi
beberapa garis plural oleh karena pengaruh medan magnetik dari luar. Gejala
ini diinterpretasikan bahwa sesungguhnya di dalam sub-kulit terdapat
beberapa sub-orbit yang mempunyai tingkat energi sama bila tanpa adanya
pengaruh medan magnetik dari luar (sehingga transisi elektronik muncul
sebagai garis tunggal), tetapi menjadi tidak sama dengan adanya pengaruh
medan magnetik dari luar. Hal ini kemudian diasumsikan bahwa revolusi
elektron dalam sub-sub orbit ini menghasilkan dua macam momen magnetik,
yaitu yang searah dan tidak-searah dengan arah medan magnetik luar, dan
keduanya ini mempunyai energi yang berbeda.
Bilangan kuantum spin, s menunjuk pada probabilitas arah
putaran elektron pada sumbunya, jadi berharga . Sedangkan bilangan
kuantum magnetik spin, ms, menunjuk pada arah putaran atau spin atau rotasi
sebuah elektron pada sumbunya, yaitu searah (clockwise) dan berlawan a n
a r a h
( a n t i c l o c k w i s e )
d e n g a n
a r a h
p u t a r
a n
j a r u m
j a m ,
d a n
o l e h
k a r e n a
i t u
d i b e
r i k a n
n i l a i
.
P a d a
t a h u n
1 9 2 1 ,
A . H .
C o m p t o n
,
s e o r a n g
f i s i k a w a n
A m e r i k a ,
s e s u n g g u h
n y a
t e l a h
m e n g u s u l k a n
s u a t u
a s u m s i
b a h
w a
e l e k t r o n
m e m p u n y a i
g e r a k
r o t a s i
p a d
a
s u m b u n y a selain gerak revolusi terhadap inti atom, dan dengan
demikian menghasilkan momen magnetik dalam. (Namun pada waktu itu, para
ilmuwan berpendapat bahwa momen magnetik hanya dimiliki oleh seluruh atom
atau molekul).
Pada tahun 1922, Otto Stern dan Walter Gerlach (fisikawan
Jerman) mengamati bahwa bila seberkas cahaya uap atom perak netral
dilewatkan dalam medan magnetik tak-homogen, ternyata berkas cahaya atom
perak ini terpisah menjadi dua bagian, berbeda dengan efek Zeeman. (Atom
perak mempunyai 47 elektron, jadi pasti ada paling tidak sebuah elektron
yang tidak berpasangan).
Pada tahun 1925, Wolfgang Pauli mengusulkan postulat bahwa
sebuah elektron dapat berada dalam dua kemungkinan keadaan atau tingkat
yang ditandai dengan bilangan kuantum spin + atau - ; dengan kata lain,
setiap orbital hanya ditempati oleh dua elektron dengan spin yang berbeda
atau antiparalel. Suatu hal yang luar biasa adalah bahwa Pauli tidak
memberikan interpretasi apapun terhadap bilangan kuantum ini. Munculnya
bilangan kuantum spin sebegitu jauh merupakan hal yang misterius, karena
ketiga bilangan kuantum yang lain, n, EMBED "Equation" \* mergeformat
,
dan m, dapat dinyatakan dalam sisten koordinat ruang sedangkan bilangan
kuantum spin tidak dapat dinyatakan dengan sistem koordinat yang manapun.
Pada tahun 1925, George Uhlanbeck dan Samuel Goudsmit
(fisikawan Belanda) menunjukkan bahwa dua keadaan elektron ini dapat
diidentifikasi dengan dua momentum sudut spin. Dengan kata lain, momentum
sudut elektron sebenarnya terdiri atas momentum sudut orbital sebagai
akibat revolusi elektron pada orbitnya, dan momentum sudut spin intrinsik
sebagai akibat rotasi elektron pada sumbunya. Kedua jenis gerak berputar
ini menghasilkan momen magnetik. Besarnya momen sudut spin ini adalah
d a l a m
u n i t
(
E M B E D
E q u a t i o n . 3
) .
M u n c
u l n y a
n i l a i

i n i
d a p a t
d i p i k i r k a n
s
e b a g a i
a k i b a t
a d a n y a
d u a
k e m u n g k i n a n
a
r a h
s p i n
e l e k t r o n ,
c l o c k w i s e
d a n
a n t i c
l o c k w i s e .
B i l a
b e r i n t e r a k s i
d e n g a n
m e d
a n
m a g n e t i k
l u a r ,
k e d u a n y a
m e m b e r i k a n
e n e r g i
y a n g
b e r b e d a ; sekalipun perbedaan ini hanya
kecil namun sudah cukup untuk menghasilkan spektrum doublet. Pada tahun
1930, P.A.M. Dirac akhirnya dapat menurunkan rumusan menurut teori
relativitas mekanika kuantum, dan ternyata bilangan kuantum spin muncul
secara natural matematis seperti halnya ketiga bilangan kuantum lainnya.
Terhadap hasil pengamatan Stern-Gerlach selanjutnya diinterpretasikan bahwa
satu elektron terluar dari separoh atom perak mempunyai arah spin yang
berlawanan dengan arah spin satu elektron dari separoh yang lain.
Kembali pada postulat Pauli tersebut dapat dinyatakan
dengan pernyataan modern bahwa total fungsi gelombang termasuk bilangan
kuantum spin dalam suatu sistem harus bersifat antisimetri terhadap saling
tertukarnya tiap dua elektron dalam sistem tersebut. Ini berarti bahwa
dalam satu sistem, tidak ada elektron yang mempunyai bilangan kuantum yang
keempat-empatnya sama.
3.9
Atom Polielektron
Sebegitu jauh, pembicaraan persamaan fungsi gelombang
Schrdinger yang dapat diselesaikan secara eksak, hanyalah berlaku untuk
atom hidrogen. Tentu saja metode penyelesaian yang sama dapat diterapkan
pada spesies isoelektronik bak-hidrogen, yaitu spesies satu elektron
seperti He+, Li2+, dan Be3+, dengan memperhitungkan harga-harga muatan inti
yang bersangkutan, Z.
Atom paling sederhana kedua adalah helium, 2He, yang
tersusun oleh satu inti atom dan dua elektron; dengan demikian terdapat
tiga interaksi yaitu satu gaya tarik elektron-1 oleh inti , satu gaya tarik
elektron-2 oleh inti, dan satu gaya tolak-menolak antara elektron-1 dan
elektron-2. Problem ketiga macam interaksi tersebut tidak dapat
diselesaikan secara eksak, tetapi dengan metode pendekatan berlanjut
(successive approximations) diperoleh hasil pendekatan dengan tingkat
akurasi yang tinggi.
Untuk atom-atom sederhana seperti helium, hal ini
tidak terlalu sukar, tetapi untuk atom-atom yang lebih berat, jumlah
interaksi menjadi makin banyak sehingga perhitungan-perhitungan menjadi
makin rumit dan melelahkan. Untuk keperluan ini digunakan metode HatreeFock atau dikenal sebagai metode medan swa-konsisten (self-consistent
field, SCF). Metode ini menyangkut proses perbaikan perhitungan fungsi
gelombang tiap-tiap elektron yang terus-menerus diulang-ulang hingga
diperoleh harga-harga yang perubahannya dapat diabaikan. Dengan metode ini
ternyata diperoleh hasil bahwa orbital-orbital dalam atom-atom selain atom
hidrogen tidak menunjukkan perbedaan yang radikal.
Perbedaan yang mendasar adalah terjadinya semacam
kontraksi (penyusutan) bagi semua jenis orbital sebagai akibat naiknya
muatan inti atom yang bersangkutan. Untuk sebagian besar tingkat energi,
perubahan naiknya energi orbital mengikuti urutan: s < p < d < f. Namun
untuk tingkat-tingkat energi yang makin tinggi oleh karena naiknya nomor
atom, perbedaan energi orbital-orbital tersebut makin tegas, dan pada
sekitar awal unsur-unsur transisi yakni nomor atom 19-22, 38-40, 56-59,
dan 89-91, penyusutan energi orbital nd dan nf terjadi secara mendadak
tidak semulus seperti penyusutan energi orbital ns dan np; hasilnya

energi orbital 3d < 4s < 4p, 4d < 5s < 5p, 4f (5d < 6s < 6p, dan 5f (6d <
7s < 7p sebagaimana ditunjukkan Gambar 3.8a-b.
3.10
Prinsip Aufbau dan Konfigurasi Elektronik
Energi elektron dalam atom terutama
ditentukan oleh energi orbital dan kontribusi energi tolakan antar
elektron. Prinsip energi minimum menyatakan bahwa elektron-elektron dalam
atom terdistribusi berdasarkan urut-urutan dari energi orbital terendah ke
tertinggi yang kemudian dikenal sebagai prinsip aufbau yang artinya prinsip
membangun. Prinsip aufbau ini biasanya didasarkan pada naiknya nilai jumlah
numerik bilangan kuantum utama dan azimut, (n + EMBED "Equation" \*
mergeformat
), sebagaimana diajukan oleh Madelung, sebagai berikut:
Orbital 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 6f 7s 7p . n 1
2 2 3 3 3 4 4 4 4 5 5 5 5 6 6 6 6 7 7 . ( 0 0 1 0 1 2 0 1 2 3 0 1 2 3 0 1
2 3 0 1 . n + ( 1 2 3 3 4 5 4 5 6 7 5 6 7 8 6 7 8 9 7 8 .
Menurut metode ini, dari kombinasi yang berbeda dapat menghasilkan
numerik yang sama, misalnya untuk 2p = 3s, 3p = 4s, dan 3d = 4p = 5s;
dalam hal ini, urutan naiknya energi ditentukan urutan naiknya nilai n.
Dengan demikian, prinsip aufbau tersebut menghasilkan urutan penataan
elektron dalam orbital sebagai berikut: 1s, 2s, 2p, 3s, 3p, 4s, 3d,
4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p, ....... .
.
Penataan elektron dalam setiap orbital menghasilkan
konfigurasi elektronik atom atau spesies yang bersangkutan. Atas dasar
pemahaman keempat bilangan kuantum dan prinsip aufbau, distribusi elektron
dalam setiap atom netral dapat ditentukan. Semua atom unsur yang telah
ditemukan telah berhasil diidentifikasi konfigurasi elektroniknya, dan
ternyata prinsip aufbau dapat diterapkan pada hampir semua atom unsur
dengan beberapa kekecualian.
SHAPE \* MERGEFORMAT
Namun harus disadari bahwa prinsip aufbau hanya tepat
untuk jumlah elektron pada tiap orbital dengan beberapa kekecualian, dan
urutan energi orbital ternyata hanya tepat untuk 20 atom unsur pertama.
Untuk atom-atom dengan nomor atom lebih besar yang melibatkan orbital d dan
f, urutan energinya ditentukan oleh bilangan kuantum utama n (Gambar 3.9a);
misalnya, energi (n-1)dx lebih rendah daripada energi ns(1-2).
Atas dasar kaidah Pauli yang menyatakan bahwa kombinasi
keempat bilangan kuantum bagi setiap elektron selalu tidak sama, maka ini
berarti bahwa setiap sub-orbital maksimum berisi dua elektron dengan spin
anti-paralel, sehingga tiap-tiap orbital maksimum berisi elektron sebanyak
2(2 EMBED "Equation" \* mergeformat
+1). Sebagai contoh, atom besi, Fe,
dengan nomor atom 26 mempunyai konfigurasi elektronik: 1s2 2s2 2p6 3s2 3p6
3d6 4s2. Perlu ditegaskan bahwa pengisian elektron (model aufbau)
bukanlah proses yang berlangsung pada suatu atom, melainkan justru yang
sesungguhnya dapat dilakukan adalah sebaliknya yaitu proses pengeluaran
elektron dari atomnya; elektron yang lebih mudah dikeluarkan adalah
elektron yang mempunyai energi yang lebih tinggi. Oleh karena itu
konfigurasi elektronik dipahami sebagai susunan elektron berdasarkan urutan
energinya (bukan berdasarkan urutan pengisiannya) yang dituliskan mulai
dari energi terendah hingga tertinggi.
Dengan demikian untuk contoh atom besi di atas, elektron
terluar (dengan energi tertinggi) adalah 4s2 (bukan 3d6) karena elektron
inilah yang memang paling rendah energi yang diperlukan untuk
mengeluarkannya; susunan demikian ini sesuai dengan diagram urutan energi
orbital (Gambar 3.9a) yang menunjukkan bahwa energi orbital 3d yang terisi
elektron tidak pernah lebih tinggi daripada energi orbital 4s; dan
demikianlah seterusnya bagi atom-atom lainnya.
Perbedaan tingkat energi antara orbital (n-1)d dengan
energi orbital ns semakin besar dengan bertambahnya elektron pada orbital
(n-1)d, sehingga urutan penulisannya juga mendahuluinya. Jadi, konfigurasi
elektronik atom Sc (dalam bentuk kondens-singkat-condense) seharusnya
dituliskan [18Ar] 3d1 4s2, dan bukan [18Ar] 4s2 3d1, demikian seterusnya
untuk yang lain sebagaimana ditunjukkan Tabel 3.7. Hal ini sangat penting
untuk pemahaman proses ionisasi, bahwa elektron yang mudah dilepas lebih
dahulu adalah elektron terluar dalam arti pula elektron dengan energi
tertinggi. Dengan kata lain, pada proses ionisasi elektron-elektron ns akan
selalu dilepas lebih dahulu sebelum elektron-elektron (n-1)d. Perubahan
energi ikat elektron terjadi pada empat daerah kritis unsur-unsur
transisi, yakni nomor atom 19-22, 37-40, 56-59, dan 88-92, sebagaimana
ditunjukkan oleh Gambar 3.9b.
Analisis spektroskopi menyarankan adanya penyimpangan atau
perkecualian dari konfigurasi elektronik menurut diagram aufbau yaitu bagi
atom kromium dan tembaga untuk seri transisi 3d. Konfigurasi elektronik
24Cr adalah [18Ar] 3d5 4s1 bukan [18Ar] 3d4 4s2 sebagaimana diramalkan oleh
aturan aufbau. Ini berarti bahwa energi konfigurasi [18Ar] 3d5 4s1 lebih
rendah (atau lebih stabil) daripada energi konfigurasi [18Ar] 3d4 4s2. Hal
ini sering dikaitkan dengan stabilitas konfigurasi elektronik setengah
penuh baik untuk orbital 3d maupun 4s. Dalam hal ini elektron-elektron
terdistribusi secara lebih merata di sekeliling inti yang mengakibatkan
energi tolakan antar-elektronnya menjadi minimum dan akibatnya energi total
konfigurasi menjadi lebih rendah. Dengan argumentasi yang sama dapat
dijelaskan bahwa konfigurasi elektronik 29Cu adalah [18Ar] 3d10 4s1 dan
bukan [18Ar] 3d9 4s2.
Perkecualian konfigurasi elektronik bagi unsur-unsur
transisi seri 4d dan 5d adalah:
Seri
4d :
41Nb : [Kr] 4d4 5s1 ; 42Mo : [Kr] 4d5 5s1 ; 44Ru :
[Kr] 4d7 5s1 ;
45Rh : [Kr] 4d8 5s1
; 46Pd
: [Kr]
4d10
; 47Ag : [Kr] 4d10 5s1
Seri
5d :
78Pt : [Xe] 4f14 5d9 6s1;
79Au : [Xe] 4f14 5d10 6s1
Tabel 3.7
Konfigurasi elektronik dan tingkat oksidasi logam periode
4
Unsur Lambang Konfigurasi
elektronik Ion yang
umum Tingkat oksidasi yang umum Kalium 19K [18Ar] 4s1 K+ +1 Kalsium 20Ca
[18Ar] 4s2 Ca2+
+2 Skandium 21Sc [18Ar] 3d1 4s2 Sc3+
+3 Titanium 22Ti [18Ar] 3d2 4s2 Ti4+
+2 , +3, +4 Vanadium 23V [18Ar]
3d3 4s2 V3+
+2 , +3, +4, +5 Kromium 24Cr [18Ar] 3d5 4s1 Cr3+
+2 , +3 ,
+6 Mangan 25Mn [18Ar] 3d5 4s2 Mn2+
+2 , +3 , +4 ,
+6 , +7 Besi 26Fe [18Ar] 3d6 4s2 Fe2+, Fe3+
+2 , +3
Kobalt 27Co
[18Ar] 3d7 4s2 Co2+, Co3+
+2 , +3 Nikel 28Ni [18Ar] 3d8 4s2 Ni2+
+2 Tembaga 29Cu [18Ar] 3d10 4s1 Cu+, Cu2+ +1, +2 Zink 30Zn [18Ar] 3d10
4s2 Zn2+
+2
Penyusunan konfigurasi elektronik menurut prinsip aufbau

tersebut akan menjadi mudah diingat jika urutan pengisian elektron
disajikan dalam suatu bentuk diagram mnemonic dalam berbagai model. Model
yang pertama kali ditemui nampaknya diusulkan oleh Pao-Fang Yi (1947),
Gambar 3.10a. Modifikasi yang paling umum terdapat dalam banyak buku teks
seperti diusulkan oleh Uncle Wiggly (1983), Gambar 3.10b.
Sejak itu, berbagai model dikembangkan sebagaimana
ditawarkan oleh Darsey (1988) dalam bentuk semacam pohon natal Pascal,
Gambar 3.10c. Model lain dengan menggunakan semacam petak anak tangga
ditunjukkan pada Gambar 3.11, dan petak papan catur dikemukakan oleh
Carpenter (1983) dan Hovland (1986).
1 1s
1s
0 2 2s
2s
0 3 2p 3s
2p 3s
1 0
4 3p 4s
3p 4s
1 0 5 3d 4p 5s
3d 4p 5s
2 1 0 6 4d 5p 6s
4d 5p 6s
2 1 0 7 4f 5d 6p 7s
4f 5d 6p 7s
3 2 1 0 8 5f 6d 7p 8s
5f 6d 7p 8s
3 2 1 0
(a)
(b)
(c) Gambar 3.11
Urutan
pengisian elektron menurut:
(a) Singh dan Dikshit (J. Chem.Ed. 1991, Vol. 68, 396)
(b) Parson (J. Chem.Ed. 1989, 66, 319)
(c) urutan bilangan kuantum, Scerri (J. Chem.Ed. 1991,
Vol. 68, 122) 2.11
Diagram Orbital Konfigurasi Elektronik
Konfigurasi elektronik sering dilukiskan dalam bentuk
diagram (kotak) orbital khususnya pada elektron terluar (outermost)
yang mengambil peran atas kharakteristik atom yang bersangkutan. Diagram
ini melukiskan kotak-kotak orbital yang kosong-isi elektron maupun arah
spinnya. Berikut ditampilkan beberapa contoh.
(1).
Atom C dengan nomor atom 6, mempunyai konfigurasi
elektronik [ H e ]
2 s 2
2 p 2 ;
b e r b a g a i
d i a g r a m
k o t a k - o r b i t a l
k o n f i g u r a s i
e l e k t r o n i k n
y a
d a p a t
d i l u k i s k a n
s e b a g a i
b e r i k u t .
2 s
2 p
!!
! ! ( c )
2 p
! !
!
!
! !
6 C :
[ 2 H e ]
!!
!
!
( b )
!!
! !
( a )
2 s
!!
!!
!!
A
C
D
E
!!
! ! ( c )
2 p
! !
!
!
! !
6 C :
[ 2
H e ]
!!
!
! ( b )
!!
! !
( a )
2 s
!!
!!
!!
B
F
G
H
D i a g r a m
A - B
m e n a t a
e l e k t r o n
s
e c a r a
m e n d a t a r ,
d a n
C - H
s e c a r a
v e r t i k a
l
d a n
m e n d a t a r ;
k e d u a n y a
s a m a - s a m a
v a l
i dnya, namun model A-B lebih efisien dalam penggunaan tempat/kertastulis. Dalam satu set mendatar seperti orbital p yang terdiri atas 3
kotak harus dipahami bahwa energi ketiganya setingkat, sehingga kehadiran
elektron dapat berada dalam kotak yang manapun, tidak harus urut alfabetik,
px-py-pz, juga sama sekali tidak harus urut numerik -1,0,+1 atau
sebaliknya, sebab harus diingat bahwa numerik ini bukanlah besaran
melainkan lambang m ! y a n g
m e l u k i s k a n
v a r i a s i
o r
i e n t a s i
d a l a m
r u a n g .
A r a h
s p i n
e l e k t r o n
p u n
d e m i k i
a n
j u g a ;
u n t u k
e l e k t r o n
n i r - p a s a n g a n
(
t a n p a
p a s a n g a n )
b o l e h
! ( )
a t a u
! ( - )
,
t e t a p i
h a r u s
p a r a l e l
d a l a m
s a t u
s e t
o r b i t a l
( s e s u a i
a t u r a n
H u n d ) ,
s e b a b
j i
k a
t i d a k
p a r a l e l
a k a n
menghasilkan energi total yang
lebih tinggi. Dalam banyak buku teks, yang paling umum dijumpai adalah
model diagram A(a) dan C, kadang B(a) dan F; yang lain barangkali tidak
pernah dijumpai.
Hal yang sama berlaku pada konfigurasi elektronik unsurunsur transisi yang melibatkan orbital d yang terdiri atas 5 kotak-orbital
sebagaimana ditunjukkan pada contoh 2 berikut.
(2). Atom V dan Fe masing-masing dengan nomor atom 23 dan
26, mempunyai konfigurasi elektronik [Ar] 3d34s2 dan [Ar] 3d64s2; diagram
kotak-orbital konfigurasi elektroniknya sering dilukiskan secara mendatar
berikut ini seperti pada A. Sementara itu banyak pula teks yang menuliskan
konfigurasi elektronik [Ar] 4s2 3d3 dan [Ar] 4s2 3d6 dengan konsekuensi
diagram orbital seperti pada B berikut ini.
3d 4s 4s 3d 23V: [18Ar] ! ! !
!!
!!
! ! !
2 6 F e :
[ 1 8 A r ]
!! ! ! ! !
!!
!!
!! ! ! ! !
A
B
D i a g r a m
A
s e s u a i
d e n g a
n
u r u t a n
e n e r g i
o r b i t a l ,
s e m e n t a r a
i t u
d i a g r a m
B
s e s u a i
d e n g a n
u r u t a n
d i a g r a m
a u f b a u
m o d e l
M a d e l u n g ,
t e t a p i
m e n y i m p a
n g
d a r i
u r u tan energi orbitalnya. Dengan demikian konfigurasi
elektronik yang dilukiskan dengan diagram B tentu saja menyesatkan.
Diagram orbital secara vertikal dan mendatar yang
mencerminkan urutan energi untuk konfigurasi elektronik 29Cu: [18Ar]
3d104s1 dilukiskan berikut ini seperti pada C, namun ada pula yang memahami
dengan konfigurasi elektronik 29Cu: [18Ar]4s13d10 dengan konsekuensi
diagram orbital seperti pada D yang tentu saja menyesatkan sebab orbital
penuh 3d10 tentu saja stabil dan energinya lebih r e n d a h
k e t i m b
a n g
4 s 1 .
4 p
4 p
! 4 s
3 d
!! !! !! !! !!
2 9 C u :
[ 1 8 A
r ]
3 d
!! !! !! !! !!
! 4 s
C
D
K o n f i g u r a s i
e l e k t r o n i k
d
e n g a n
d i a g r a m
A
d a n
C
s a n g a t
m u d a h
d i p
a h a m i
k e t i k a
t e o r i
i k a t a n
v a l e n s i
m e
njelaskan misalnya terjadinya hibridisasi sp3 pada ion Fe(II) dalam
kompleks [FeCl4]2-, dan pada Cu(II) dalam [CuCl4]2-, sebab orbital kosong
4s pada kedua ion ini bergabung dengan orbital kosong terdekat berikutnya
yakni 4p. Diagram B dan D tentu kesulitan menjelaskan terjadinya (segala
bentuk) hibridisasi demikian ini.
Pertanyaan yang segera muncul pada konfigurasi elektronik
orbital d yang belum penuh seperti pada [Ar] 3d34s2 (atau yang sejenis)
adalah, mengapa konfigurasi elekroniknya bukan [Ar] 3d54s0 atau [Ar]
3d44s1, jika memang energi orbital 3d < 4s? Demikian pula misalnya mengapa
konfigurasi elektronik Fe bukan [Ar] 3d84s0?
Jawaban utama terkait dengan orbital-radial (jarak) 3d versus 4s
sebagaimana disajikan pada Gambar 3.12. Orbital-radial ini menunjukkan
bahwa probabilitas rapatan elektron pada orbital 4s ternyata berupa empat
gundukan (dengan 3 simpul-nodal), dua diantaranya tumpang-tindih berada
dalam daerah probabilitas rapatan 3d, dan bahkan terdapat satu gundukan
kecil yang lain lebih dekat dengan inti ketimbang 3d, namun satu gundukan
utama jauh berada di luar 3d; keadaan demikian ini sering dikatakan orbital
4s mempunyai efek penetrasi (penembusan) terhadap 3d. Jadi, sangat jelas
bahwa rerata probabilitas rapatan elektron orbital 3d memang lebih dekat
dengan inti daripada 4s yang berarti energi 3d < 4s. Akan tetapi daya
penetrasi orbital 4s mengakibatkan perbedaan energi antara keduanya

berkurang, dan bahkan hadirnya gundukan kecil pertama diduga berperan
secara signifikan atas pemilihan elektron menempati orbital 4s ketimbang 3d
untuk nomor atom 19-20 (K-Ca). Dengan demikian dapat dipahami bahwa untuk
unsur-unsur transisi elektron elektronnya tidak serta-merta semua
menempati orbital 3d begitu saja.
Gambar 3.12
Gambar orbital 3d versus 4s menunjukkan efek penetrasi 4s,
namun probabilitas jarak rata-rata 3d lebih dekat dengan inti.
Analisis spektroskopi menunjukkan bahwa pelepasan elektron pertama dari
unsur-unsur transisi netral ternyata menghasilkan ion dengan konfigurasi
elektronik yang mengurangi bahkan mengosongkan elektron dalam orbital 4s
sebagaimana persamaan berikut:
21Sc: [Ar]3d14s2
21Sc+:
[Ar]3d14s1
22Ti: [Ar]3d24s2
22Ti+: [Ar]3d24s1
23V: [Ar]3d34s2
23V+: [Ar]3d4
24Cr: [Ar]3d54s1
24Cr+: [Ar]3d5
26Fe: [Ar]3d64s2
26Fe+: [Ar]3d7
27Co: [Ar]3d74s2
27Co+: [Ar]3d8
28Ni: [Ar]3d84s2
28Ni+: [Ar]3d9
29Cu: [Ar]3d104s1 EMBED "Equation" \* mergeformat
29Cu+: [Ar]3d10
57La: [Xe]5d14s2
57La +: [Xe]5d2
Nah, apa yang dapat disimpulkan data tersebut? Pelepasan 1
elektron dari 4s2, ternyata banyak ditemui tidak menyisakan 4s1, melainkan
terjadi penambahan / perpindahan ke orbital 3d, dan ini tentu berarti
menghasilkan energi yang lebih rendah.
Jadi data tersebut menyarankan
bahwa energi orbital (n-1)d < ns, dan ini sesuai dengan hasil mekanika
kuantum, bertentangan dengan anggapan diagram aufbau yang benar-benar
menyesatkan tidak hanya pada teks general, tetapi juga teks advanced
(Scerri, 1989). Orbital-radial yang menunjukkan penetrasi berkelanjutan 6s
atas 5d atas 4f ditampilkan pada Gambar 3.13. Rerata rapatan elektron 4f
yang secara berturut-turut jauh lebih dekat dengan inti ketimbang 5d lalu
6s menunjukkan naiknya energi orbital yang bersangkutan.
2.12
Efek Perisai dan Penetrasi

Sebagaimana telah dibicarakan perihal prinsip aufbau,
perlu kiranya diketahui bagaimana energi orbital-orbital berbeda dengan
energi orbital-orbital atom hidrogen.
Untuk atom berelektron banyak
artinya lebih dari satu, setiap elektron dalam orbitalnya mengalami gaya
tarik Coulomb ke arah inti atom dan gaya tolak Coulomb dari semua elektron
lainnya; sekumpulan elektron yang lain ini diasumsikan membentuk rerata
medan yang dapat dipandang sebagai titik bermuatan negatif dan terpusat di
dalam inti atom.
Dengan demikian setiap elektron mengalami suatu medan
pusat tunggal dari inti atom dan titik muatan negatif yang berasal dari
rerata kumpulan elektron lainnya tersebut. Dapat dipahami bahwa titik
muatan negatif ini tentu akan mengurangi muatan inti dari harga yang
"sesungguhnya", Z e, menjadi muatan inti efektif, Zef e, terhadap satu
elektron tertentu, di mana makin dekat dengan inti akan mengalami harga Zef
makin besar. Pengurangan ini disebut sebagai efek tameng atau
p e r i s a
i
a
g
e
p e r
e r h
Z e f
t
f
i
a
a
f
s
d
p
p
p
g
i
r
s
l
a
a
e
n
,
a
e k
m
t
d e
g a
S
g a
a
a
l
o
e
e
d
d
s
a
n
b
u
s a
e c t )
a i ,
a p
m
=
Z
t
u
a
r
n
l
i
r
l
h
h
o
a
u
a
k
a t
b
( 1 )
t
u r u t a n
r i n g
(
,
d a n
s,
m e r
u a t a n
s.
P e n e t a
n
d a l a
n y a
d i
n
1 9 3 0
n a ;
d e
u a n t u m
e r
m e n
e r i k u t
E l e k t r
( 1 s ) ,
s
p
u
i
h
a
p
n
i
r
a
t
e l d i
a m e t
k a n
i
m e
p a n
m
o r
p e l o
b u k
n g a n
n ,
g e m u
:
o n
d
( 2 s ,
h
b
p
a
a
i
o
n
m
l,
k a
n
e
f
n
r
t
r
l
e
g
a
i
a
m
d
k a
g
a
r
a
a k t
u r u
t a u
s
t a u
t
o r
k o
t
h u b
c
e
r
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J J J Ff G
$ If
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J J J J K K K FfL
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$ $ If a$ gd1+ K K
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$ If gdS$
$ dh a$ gdsw1
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M M M N N N N O O O 0O 2O NO XO xP
w h?[ h 6
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$ If a$ gd1+
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$ $ If a$ gdS$ T zV ,X .X 0X 2X 4X 6X 8X :X <X @X BX DX FX HX JX LX NX
PX RX XX ZX
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$ dh a$ gd V V V V V V V V V V V V V W W ]W _W aW dW fW hW
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rX tX vX xX zX |X X X X X X X X X X X X

$ If gd- n Ffy
$ $ If a$ gd- n zX |X X X X X X X X X X X X X X X X X X
X X X X X X X X X X X X X X X X X X X X Y Y Y Y Y Y Y Y
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dh x @& ` gd=/ $ dh x @& a$
gd=/
$ dh a$ gd
$ dh x a$ gd,sE Ffo $ dh $ If a$ gd1+ Y Y (Y *Y ,Y .Y 6Y 8Y
Z Z *Z ,Z -Z RZ SZ TZ VZ sZ tZ uZ wZ Z Z Z Z Z Z Z Z Z [ +
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)[ [ [ [ [ [ [ [ [ [ \ \ \ \ \ \ \ \ \ \ \ \ \ 3\ 4\ 8\ 9\ :\ ;\
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hgW 6
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habe habe habe

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habe 6
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j h=/ 5
U
h=/ 5
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hlS 6
..a na gb b c
d d e h 'h fm o q ' {

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$ dh x a$ gd)
dh x gd)
dh x @& gdJD9
$ dh a$ gdV=
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c
c
c
c c c
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c c c c c c c c c c c c c c
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V
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he 6
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h?A(
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h 5
B2p), (3s, 3p), (3d), (4s, 4p),
(4d), (4f ),
dan seterusnya; ns dan np dipertimbangkan dalam satu kelompok.
(2)
Elektron dalam kelompok di atasnya tidak menamengi sama
sekali elektron yang
bersangkutan.
(3)
Faktor perisai sebesar 0,35 berlaku satu sama lain bagi
elektron-elektron dalam
kelompok yang sama, kecuali bagi
elektron-elektron 1s faktor ini hanya sebesar
0,30.
(4)
Elektron-elektron d dan f mengalami penamengan dengan
faktor perisai sebesar
1,00 dari setiap elektron yang terletak
dalam kelompok bawahnya.
(5)
Elektron-elektron ns dan np mengalami penamengan dengan
faktor perisai
sebesar 0,85 dari setiap
elektron yang terletak dalam kelompok (kulit) langsung
di
bawahnya (n-1), dan sebesar 1,00 dari setiap elektron yang terletak lebih
lanjut
di bawahnya.
Idealnya, aturan tersebut menghasilkan energi yang besarnya sesuai dengan
rumusan :
E = ( EMBED Equation.3
) 13,6 eV
..............
(3.8)
Sebagai contoh, muatan inti efektif bagi elektron valensi
dalam a t o m
7 N
d e n g a n
p e n g e l o m p o k a n
( 1 s 2 )
( 2 s 2 ,
2 p 3 ) ,
a d a l a h
:
Z e f
=
Z
s =
7
[
( 2
x
0 , 8 5 )
+
( 4
x
0 , 3 5 ) ]
=
7
3 , 1
=
3 , 9 .
D e m i k i a n
j u g a
m u a t a n
i n t i
e f e
k t i f
b a g i
e l e k t r o n
4 s
d a l a m
a t o m
3 0 Z n
d e n g a n
p e n g e l o m p o k a n
( 1 s 2 )
( 2 s 2 ,
2 p 6
)
( 3 s 2 , 3 p 6
)
( 3 d
1 0 )
( 4 s 2 ) ,
a d a l a h
:
Z e f
=
Z
s =
3 0
[ ( 1 0
x
1 , 0 0 )
+
( 1 8
x
0 , 8 5 )
+
( 1
x
0 , 3 5 ) ]
=
3 0
2 5 , 6 5
=
4
, 3 5 .
S e d a n g k a n
m u a t a n
i n t i
e f e k t i f
b a g i
e l
e k t r o n
3 d
a d a l a h
:
Z e f
=
Z
s =
3 0
[ ( 1 8
x
1 , 0 0 )
+
( 9
x
0 , 3 5 ) ]
=
3 0
2 1 , 1 5
=
8 , 8 5
P e r h i t u n g a n
S l a t e r
k u r a n g
b e g
i t u
a k u r at antara lain karena mengasumsikan bahwa semua orbital s,
p, d, atau f memberikan daya perisai yang sama kuat terhadap elektronelektron di atas-nya; tentu saja hal ini tidak sesuai dengan pola
distribusi radial masing-masing orbital (Gambar 3.12, 3.13 dan 3.14).
Clementi dan Raimondi (1963) memperbaiki cara perhitungan berdasarkan
fungsi gelombang medan swa-konsisten, SCF, dari atom hidrogen hingga
kripton. Dengan Nn l m e r u p a k a n
j u m l a h
e l e k t r o n
d
a
t
g
n
l a m
o b
u k
p e r
i
s e t i
g g a
4 p
s1
( N 2 s
+
s , p )
s2
1
+
N
)
s2
1
)
s )
i t a l
n l,
b
h i t u n g a n
t
a p
e l e k t r o
a d a l a h
s e
s
=
0 , 3
N 2 p )
+
0
0 , 0 0 4 8
s3
1
+
N
d
+
0
s3
1
)
+
0 , 1 5 5 8
s4
1
)
+
s3
1
)
s4
1
)
N 3 d
s
=
3 p )
, 1 9 7
p
=
0 , 0
N 4 p
s
=
0 , 8
d
=
p
=
s
=
2 p )
p
=
0 , 0 7 7 3
e n t u k
r u m u
e t a p a n
p e r
n
d a l a m
o r
b a g a i
b e r i
( N 1 s
1 )
, 0 1 5 8
( N 3 s
s a
i s
b i
k u
+
, p
n
u m u m
a i ,
s,
t a l
1 s
t
:
0 , 0 0 7 2
, d
+
u n
b a
h i
N 4
1 , 7 2 0 8
0 , 2 0 6 2
+
0 , 3 6 0 1
( N 3 s , p , d
+
( N 2 s
N 4 s , p
2 , 5 7 8 7
N 3 s
-
+
0 , 3 3 2 6
0 , 0 1 6 1
( N 3 p
( N 2 p
+
N 4
0 , 0 0 8 5
N 4 p
8 , 4 9 2 7
+
0 , 2 5 0 1
( N 3 s
+
0 , 0 7 7 8
N 4 s
+
0 , 3 3 8 2
N 3
8
N 4 p
9 , 3 3 4 5
+
0 , 3 8 0 3
( N 3 p
5 2 6
N 4 s
+
0 , 3 2 8 9
N 3 d
+
-
1 5 , 5 0 5
4 3 3
N 3 d
+
1 3 , 5 8 9 4
0 , 1 0 6 5
N 4 p
2 4 , 7 7 8 2
0 , 0 9 7 1
( N 4 s
0 , 0 6 8 7
N 4 p
+
0 , 2 6 9 3
( N 3 d
0 , 2 9 0 5
( N 4 p
S e b agai contoh, muatan inti efektif untuk elektron 2p

dalam atom 7N adalah, Zef = 3,756 , dan untuk elektron 4s dan 3d dalam
atom 30Zn, masing-masing adalah 5,965 dan 13,987. Harga-harga yang
diperoleh dari rumusan Clementi dan Raimondi ini sangat dekat dengan hargaharga yang lebih akurat dari aplikasi langsung fungsi gelombang SCF
sebagaimana ditunjukkan dalam Tabel 3.8. Metode Clementi dan Raimondi ini
lebih realistik daripada metode Slater karena memperhitungkan sifat
penetrasi elektron dalam orbital yang terletak lebih luar.
Gambar 3.14
Grafik berbagai fungsi
distribusi radial melukiskan
tingkat penetrasi orbital s, p, dan d.
Satu cara alternatif lain untuk melukiskan muatan inti
efektif yang berlaku bagi suatu elektron tertentu adalah konsep penetrasi
(penembusan) yang sekaligus dapat dipakai untuk rasionalisasi perbedaan
energi orbital. Sebagaimana dilukiskan grafik peluang fungsi radial (Gambar
3.12 - 3.14), daya penetrasi orbital ke arah inti atom secara umum
mengikuti urutan s > p > d > f. Misalnya orbital 2s dan 2p, keduanya
menembus ke dalam orbital 1s, artinya beberapa bagian rapatan elektron 2s
dan 2p terletak di dalam daerah rapatan elektron 1s. Apabila dilakukan
perhitungan secara teliti, orbital 2s ternyata menembus sedikit lebih besar
daripada orbital 2p. Hal ini menyarankan bahwa rapatan elektron 2s akan
ditamengi sedikit lebih lemah (terhadap pengaruh muatan inti) daripada
rapatan elektron 2p; selain itu dapat pula dipahami bahwa orbital 2s lebih
stabil atau mempunyai energi sedikit lebih rendah daripada orbital 2p
apabila orbital 1s berisi ekektron. Secara sama penetrasi orbital d dan

f dapat diterangkan.
Tabel 3.8
Muatan inti efektif, Zef , hingga unsur ke 36
Unsur 1s 2s 2p 3s sp 4s 3d 4p 1H 1,00
2He 1,69
3Li 2,69
1,28
4Be 3,68 1,91
5B 4,68 2,58 2,42
6C 5,67 3,22 3,14
7N 6,66 3,85 3,83
8O 7,66 4,49 4,45
9F 8,65 5,13 5,10
10Ne 9,64 5,76 5,76
11Na 10,63 6,57 6,80 2,51
12Mg 11,61 7,39
7,83 3,31
13Al 12,59 8,21 8,96 4,12 4,07
14Si 13,57 9,02 9,94 4,90
4,29
15P 14,56 9,82 10,96 5,64 4,89
16S 15,54 10,63 11,98 6,37 5,48
17Cl 16,52 11,43 12,99 7,07 6,12
18Ar 17,51 12,23 14,01 7,76 6,76
19K 18,49 13,00 15,03 8,68 7,73 3,50
20Ca 19,47 13,78 16,04 9,60 8,66
4,40
21Sc 20,46 14,57 17,06 10,34 9,41 4,63 7,12
22Ti 21,44 15,38
18,07 11,03 10,10 4,82 8,14
23V 22,43 16,18 19,07 11,71 10,79 4,98 8,98
24Cr 23,41 16,98 20,07 12.37 11,47 5,13 9,76
25Mn 24,40 17,79 21,08 13,02
12,11 5,28 10,53
26Fe 25,38 18,60 22,09 13,68 12,78 5,43 11,18
27Co
26,34 19,41 23,09 14,32 13,44 5,58 11,86
28Ni 27,35 20,21 24,10 14,96
14,09 5,71 12,53
29Cu 28,34 21,02 25,10 15,59 14,73 5,86 13,20
30Zn
29,32 21,83 26,10 16,22 15,37 5,97 13,88
31Ga 30,31 22,60 27,09 17,00
16,20 7,07 15,09 6,22 32Ge 31,29 23,36 28,08 17,76 17,01 8,04 16,25 6,78
33As 32,28 24,13 29,07 18,60 17,85 8,94 17,38 7,45 34Se 33,26 24,89 30,06
19,40 18,71 9,76 18,48 8,29 35Br 34,25 25,64 31,06 20,22 19,57 10,55 19,56
9,03 36Kr 35,23 26,40 32,05 21,03 20,43 11,32 20,63 9,77
C.
Latihan Kegiatan Belajar-3
Petunjuk:
Selesaikan soal-soal berikut dengan penjelasan singkat
menurut bahasa Anda sendiri.
1.
Beri batasan tentang: (a) orbital, (b) aturan Hund, (c) prinsip
larangan Pauli
2.
Tentukan kemungkinan seperangkat bilangan kuantum bagi elektron
yang
menempati bilangan kuantum utama, n = 4
3.
Tentukan nilai terendah bilangan kuantum utama (n) untuk m EMBED
= +4
4.
Identifikasi orbital mana yang mempunyai nilai n = 5 dan
= 1, demikian juga
n = 6 dan
= 0
5.
Bagaimana hubungan antara masing-masing bilangan kuantum utama
(n) dan
dengan sifat
orbital
6.
Kembangkan berbagai kemungkinan diagram mnemonic model papan
catur untuk konfigurasi elektron (Jawaban Anda dapat diklarifikasi dengan
referensi (1) Monaghan, P. K., and Coyne, M., Education in Chemistry,1988,
September, 139; (2) Carpenter, A. K. 4s, 3d, What?. Journal of Chemical
Education, 1983, Vol. 60, 562, dan (3) Hovland, A. K. Aufbau on a
Chessboard. Journal of Chemical Education, 1986, Vol. 63, 607).
7.
Jelaskan secara singkat mengapa atom 4Be mempunyai konfigurasi
elektronik
1s2 2s2, bukan 1s2 2s1 2p1
8.
Tulis konfigurasi elektronik spesies-spesies berikut dengan
menggunakan atom
gas mulia sebagai konfigurasi elektronik inti-nya :
11Na , 28Ni, 29Cu, 20Ca, 24Cr, dan 82Pb.
21Sc3+, 29Cu2+, 19K+, 17Cl-, 27Co2+, dan 25Mn4+
9.
Apa yang dimaksudkan dengan muatan inti efektif, efek penetrasi,
dan efek
Perisai.
Bagaimana pula urutan besarnya efek perisai orbital secara
umum?
10. Hitung muatan inti efektif (Zef ) terhadap elektron 2p menurut Slater
dalam atom
atom 6C, 7N, dan 8O. Bandingkan kenaikan muatan inti efektif dari N
ke O dengan kenaikan dari C ke N , dan jelaskan mengapa demikian?
11.
Selidiki kenaikan muatan inti efektif untuk elektron 2s dari at
o m
L i
B e ,
d e m i k i a n
j u g a
u n t u k
e l e k t r o n
2 p
d a r i
a t o m
B
C ;
m a n a
y a n g
l e b i h
b e s a r
k e n a
i k a n n y a ,
d a n
j e l a s k a n
m e n g a p a
d e m i k i a n
.
D .
R a m b u - r a m b u
K u n c i
J a w a b a n
L a t i h a n
K e g i a t a n
B e l a j a r - 3
1 ( a )
O r b i t a l
a t o m
a d a l a h
g a m b a r a n
p e l u a n g
m e n d a p a t k a n
e l e k t r o n
( Y2 )
a t a u
g a m b a r a n
f u n g s i
g e l o m b a n g
e l e k t r o n
i t u
s e n d i r i
( Y)
d i
s e p u t a r
i n t i
a t o m .
Y a n g
p a l i n g
u m u m
o r b i t a l
a t o m
d i g a m b a r k a n
s
e b a g a i
f u n g s i
g e l o m b a n g
s u d u t .
H i n g g a
k i n i
d i k e n a l
a d a n y a
o r b i t a l
s ,
p ,
d ,
d
a n
f .
A t u r a n
H u n d
m e n y a t a k a n
b a h w a
e l e k t r o n
- e l e k t r o n
d a l a m
mengisi orbital cenderung dengan spin
paralel tanpa berpasangan lebih dahulu.
Prinsip larangan Pauli menyatakan bahwa elektron dalam menempati orbital
tidak mungkin memiliki keempat bilangan kuantum sama secara serentak; jadi
dalam setiap orbital maksimum hanya menampung 2 elektron dengan bilangan
kuantum spin yang berlawanan atau anti paralel.
2.
Elektron pada n = 4, seperangkat bilangan kuantum yang mungkin
adalah:
Orbital 4s:
n = 4,
= 0,
m EMBED "Equation" \* mergeformat
= 0, s = +
dan
n = 4,
= 0, m EMBED "Equation" \* mergeformat
= 0, s = -
Orbital 4p:
n = 4,
EMBED
=
0, s = +
dan
n = 4,
= 0, s = -
n = 4,
EMBED "Equation" \*
mergeformat
= -1, s = +
dan
n = 4,
= 1, m EMBED
= -1, s = -
n = 4,
= 1,
= +1, s = + dan
n = 4,
EMBED
=
+1, s = -
Orbital 4d:
n = 4,
= 2,
= 0, s = +
dan
n = 4,
= 0, s = -
n = 4,
= -1, s = +
dan
n = 4,
= 2,
= -1, s = -
n = 4,
= +1, s = +
dan
n = 4,
= +1, s = -
n = 4,
EMBED "Equation" \*
mergeformat
= -2, s = +
dan
n = 4,
= 2, m EMBED
= -2, s = -
n = 4,
= 2,
= +2, s = + dan
n = 4,
EMBED
=
+2, s = -
Orbital 4f:
n = 4,
= 3,
= 0, s = +
dan
n = 4,
= 0, s = -
n = 4,
= -1, s = +
dan
n = 4,
= 3,
= -1, s = -
n = 4,
= +1, s = +
dan
n = 4,
= +1, s = -
n = 4,
EMBED "Equation" \*
mergeformat
= -2, s = +
dan
n = 4,
= 3, m EMBED
= -2, s = -
n = 4,
= 3,
= +2, s = + dan
n = 4,
EMBED
=
+2, s = -
n = 4,
EMBED "Equation" \*
mergeformat
= -3, s = +
dan
n = 4,
= 3, m EMBED
= -3, s = -
n = 4,
= 3,
= +3, s = + dan
n = 4,
EMBED
=
+3, s = -
3.
Nilai terendah bilangan kuantum utama (n) untuk m EMBED
= +4 adalah: n = 5, sebab
nilai n ini mencakup nilai m EMBED "Equation" \* mergeformat
dari 0 hingga 4.
4.
Orbital yang mempunyai nilai n = 5 dan
EMBED "Equation" \*
mergeformat
= 1 adalah 5p, dan yang mempunyai
n = 6 dan
= 0 adalah 6s.
5.
Hubungan antara masing-masing bilangan kuantum utama (n) dan
dengan sifat orbital adalah bahwa:
(1)
besarnya nilai n menunjukkan banyaknya macam nilai
EMBED
dan juga orbital; untuk n = 1 hanya ada satu
nilai
yakni nol, dan 1 orbital (s);
untuk n = 2 ada 2 nilai
yakni nol dan
1, dan 2 macam orbital yakni s ( EMBED "Equation" \* mergeformat
= 0)
dan p ( EMBED "Equation" \* mergeformat

= 1); n = 3 ada 3 macam nilai
(0, 1, 2) dan 3 macam orbital s, p, d,
dst.
(2)
untuk
bernilai genap,
orbital bersifat simetri, dan untuk
bernilai gasal orbital bersifat anti simetri.
6.
Kemungkinan diagram mnemonic model papan catur untuk penyusunan
konfigurasi elektron:
1s
2s
2p 3s
3p 4s
7s 8s
3d 4p 5s
5s 6s 6p 7p
4d 5p 6s
3s 4s 4p 5p 5d 6d
4f 5d 6p 7s
1s 2s 2p 3p 3d 4d 4f 5f
5f 6d 7p
8s Diagram mnemonic urutan pengisian elektron pada orbital model menaiki
(kiri) dan menuruni (kanan) 2 tahapan.
1s
2s
2 p
3 s
3 p
4 s
3 d
4 p
5 s
4 d
5 p
6 s
4 f
5 d
6 p
7 s
5 f
6 d
7 p
8 s
D i a g r a m
m n e m
o n i c
p e n g i s i a n
e l e k t r o n
p a d a
o r b i t a l
( d i b a c a
k e
k a n a n
d a r i
a t a s
k e
b a w a h )
m e n u r u t :
P r o f .
E .
S t e e l
( d a l a m
M o n a g h a n
&
C o y n
e ,
1 9 8 8 )
1 s
! !
5 f
6 d
!
4 f
5 d
6 p
7 s
4 d
5 p
6 s
4 s
5 s
5 s
5 p
5 d
6 s
6 p
6 d
2 p
3 s
s
8 s
( b )
D i a g r a m
m n e m
pada orbital menurut:
dari kiri ke kanan)
7 p
4 p
5 f
1 s
o n
8 s
2 s
2 p
!
3 s
3 p
3 d
! !
4 d
4 f
!
3 d
4 p
3 p
4 s
7 s
7 p
2
( a )
i c
urutan pengisian elektron
(a) Carpenter (dibaca ke bawah
(b) Hovland (dibaca ke kanan

dari bawah ke atas)
7.
Atom 4Be mempunyai konfigurasi elektronik 1s2 2s2, bukan 1s2 2s1
2p1, sebab energi orbital 2s lebih rendah daripada energi orbital 2p, dan
energi tolakan antar elektron dalam orbital 2s2 masih lebih rendah dari
total energi (konfigurasi) 2s1 2p1.
8.
Konfigurasi elektronik:
a.
11Na : [10Ne] 3s1;
28Ni:
[18Ar]
3d8 4s2;
29Cu:
[18Ar] 3d10 4s1;
20Ca:
[18Ar] 4s2;
24Cr:
[18Ar]
3d5 4s1;
82Pb:
[54Xe] 4f14 5d10 6s2 6p2
b.
21Sc3+: [18Ar];
29Cu2+: [18Ar]
3d9;
19K+:
[18Ar]
17Cl-:
[18Ar];
27Co2+: [18Ar] 3d7;
25Mn4+: [18Ar] 3d3
9.
Muatan inti efektif (Zef.) adalah muatan inti sesungguhnya yang
dirasakan oleh elektron yang bersangkutan setelah muatan inti (Z)
dikurangi-dikoreksi oleh efek perisai ( s)
d a r i
e l e k t r o n - e
l e k t r o n
y a n g
l a i n ,
Z e f
=
Z
s
E f e k
p e n e t r a s i
a d a l a h
e f e k
i n t e r a k s i
d a r i
e l e k t r o n
d a l a m
o r b i t a l
y a n g
l e b i h
t i n g g i
e n e r g i n y a
n a m u n
o r b i t a l
i n i
s e s
u n g g u h n y a
m e n e m b u s
k e
d a e r a h
o r b i t a l
y
a n g
l e b i h
r e n d a h
e n e r g i n y a
s e h i n g g a
i n
t e r a k s i
m u a t a n
i nti terhadap elektron dalam orbital yang
lebih rendah energinya ini menjadi berkurang.
Efek perisai adalah efek interaksi dari elektron dalam orbital yang lebih
rendah energinya dengan muatan inti sehingga interaksi muatan inti terhadap
elektron dalam orbital yang lebih tinggi energinya menjadi berkurang.
Urutan besarnya efek perisai orbital secara umum adalah orbital s>p>d>f.
10.
Muatan inti efektif terhadap elektron 2p dalam atom-atom:
6C:
Zef = 6 [2,5787 + 0,3326] = 3,0887
7N:
Zef = 7 [2,5787 + (2 x 0,3326)] = 3,7561
8O:
Zef = 8 [2,5787 + (3 x 0,3326)] = 4,4235
Kenaikan muatan inti efektif dari atom N ke atom O sama dengan kenaikannya
dari atom C ke atom N yakni 0,6674, sebab masing-masing memberikan efek
perisai dari satu elektron yang sama yakni dalam orbital 2p.
11.
Muatan inti efektif terhadap elektron 2s untuk atom
Li adalah Zef = 3 (1,7208) = 1,2792, dan
Be adalah Zef = 4 [1,7208 + 0,3601] = 1,9191; jadi terdapat kenaikan
0,6399.
Muatan inti efektif terhadap elektron 2p untuk atom
B adalah Zef = 5 [2,5787] = 2,4213, dan
C adalah Zef = 6 [2,5787 + 0,3326] = 3,0887; jadi terdapat kenaikan
0,6674.
Jadi kenaikan muatan inti efektif untuk atom B-C lebih besar daripada
kenaikan muatan inti efektif untuk atom Li-Be, sebab untuk B-C terjadi
penambahan elektron 2p sedangkan untuk Li-Be terjadi penambahan elektron 2s
dengan efek perisai yang lebih rendah ketimbang efek perisai orbital 2p.
Struktur Atom dan Sistem Periodik Unsur.
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S u g i y a r t o
P A G E
1 . P A G E
3 8
f x ( z 2
P 4
P 3
P 2
P 1
x +
z +
O
y 2 )
y +
q
f
r
P
G a m b a r
3 . 5
S e b u a h
dalam sistem koordinat Cartes
dan koordinat kutub - bola
t i t ik P (elektron)
Sumber cahaya
Gambar 3.13
(a)
+
3300
3000
2700
2400
2100
1500
1200
900
600
300
3600
3300
3000
Orbital-radial
4f, 5d, dan 6s
2700
2400
2100
1800
1500
1200
900
600
300
00
(b)
+
+
3600
00
3300
3000
2700
2400
2100
1500
1200
900
(a)
= foton
= elektron
= penembak elektron
mikroskop
(d)
(c)
(b)
Gambar 3.4
Ketidakpastian posisi dan kecepatan sebuah elektron oleh
karena efek tumbukan dengan foton cahaya
Gambar 3.1
Contoh pembelahan garis spektrum dalam medan magnetik
dalam medan magnetik

tanpa medan magnetik
Garis-garis spektrum
600
300
3300
3000
2700
2400
2100
1800
1500
1200
900
600
300
(c)
Gambar 3.6
Kertas grafik polar (a), dan bentuk orbital
polar: fungsi cos
( b )
d a n
f u n g s i
c o s 2
( c )
a t a u
o r b i t a l
p z
( b e b
e r a p a
t i t i k
n i l a i
0 - 9 0 0
d i g a m b a r k a n )
y +
x +
z +
+
+
+
+
f y ( z 2
x 2 )
y 2 )
y +
x +
z +
+
+
+
+
f z ( x 2
y +
x +
z +
+
+
+
+
y +
x +
z +
+
+
+
+
fxyz
Gambar
1
20
40
60
80
100
n = 1
3.9a
Diagram energi orbital atom sebagai fungsi nomor atom
n = 2
n = 3
n = 4
n = 5
n = 6
n = 7
1s
2p
2s
5d
5p
5s
6p
6s
7p
7s
6d
5f
4f
4d
4p
4s
3d
3p
3s
=
=
=
=
f
d
p
s
E n e r g i
Nomor atom
Gambar 3.9b
37
Rb
38
Sr
39 40
Perubahan energi ikat elektron (binding) versus nomor atom
Zr Nb
41
4d
4d
5s
5s
5p
5p
56
Ba
57
La
58 59
Ce
Pr
4f
4f
5d
6s
6s
5d
5,0
10,0
0
19
K
20
Ca
21
Sc
22
Ti
3d
3d
4s
4s
4p
4p
87
Fr
88
Ra
89 90
Ac
91
Th Pa U
92
5f
5f
6d
7s
7s
6d
Energi / eV
Nomor Atom
5f
(a)
(17)
(16)
(15)
(14)
(13)
(12)
(11)
(10)
(9)
(8)
(7)
(6)
(5)
(4)
(3)
(2)
(1)
4f
3d
4d
5d
6d
2p
3p
4p
5p
6p
1s
3s
4s
5s
6s
7s
2s
(c)
5f
6d
7p
8s
3d
4p
5s
4f
5d
6p
7s
4d
5p
6s
2p
3s
3p
4s
2s
1s
(b)
1s
2s
3s
4s
5s
6s
7s
2p
3p
4p
5p
6p
7p
3d
4d
5d
6d
4f
5f
Gambar 3.10
Diagram R T V X Z \ ^ ` b d f h j l n p r
t v x z | ~
R T X \ ^ ` b d f l n p t v x z | ~

~~
hc CJ \
hc CJ OJ QJ \
hc 5
CJ \
]
hc 5
]
hc 5
CJ H* ]
hc 5
6
hc 5
CJ H* \
hc 5
CJ H* \
hc 5
CJ \
hc CJ EH H* ]
hc CJ EH H* ]
hc H* ]
hc 6
H*
hc 6
hc hhX 0

" $ & ( * , . 0 2 4 6 8 :
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N P R T V X r t z |
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$ a$ gd?A(
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OJ
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hu hc 5
hq4 6
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CJ ]
hc hc mH sH hc mH sH hc 5
CJ \
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6
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2

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h[ hc CJ ]
h9 hc 6
h9 hc CJ h9 hc 6
CJ h[ hc CJ h[ hc 6
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CJ h$ hc CJ aJ hc hc hc mH sH =

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hM hc 5
6
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h[ hc 6
h[ hc CJ hc h[ hc CJ ]
h[ hc 6
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hc 6
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6
< mnemonic urutan pengisian elektron pada orbital menurut:
Pao-Fang Yi (J. Chem. Ed. 1947, Vol. 24, 567)
Uncle Wiggly (J. Chem. Ed. 1983, Vol. 60, 562)
(c)
Darsey sebagai pohon natal Pascal( (J. Chem. Ed. 1988, Vol. 65,
1036)
Gambar 3.2
orbit elektron model
Kemungkinan bentuk
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<div class="header" id="header_top"><img src="index_icons/winxp/hd3.

menuliskan konfigurasi elektronik atom unsur dengan prinsip aufbau, aturan

elektron daripada energi sistem.

bilangan kuantum azimut atau bilangan kuantum sekunder dengan notasi

mendapat kesulitan dalam melukiskan sifat karakteristik cahaya. Banyak

teori relativitas Einstein. Dengan mengingat kembali hubungan massa dengan

untuk membuat model visualisasi tentang atom, melainkan berupa deskripsi

Sebaliknya agar elektron dapat terlihat jelas posisinya

terhadap inti yang mempunyai muatan Z

Orbital 1s mempunyai fungsi gelombang yang berharga

(a) Fungsi gelombang dengan

tidak semulus seperti penyusutan energi orbital ns dan np; hasilnya

Penyusunan konfigurasi elektronik menurut prinsip aufbau

penetrasi orbital 4s mengakibatkan perbedaan energi antara keduanya

Efek Perisai dan Penetrasi

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hr8! H* hr8! CJ EH hr8! hr8! 6

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h': CJ H* h': CJ EHaJ

h` h?A( h?A( h` h?A( 6

$ $ If a$ gd1+ $ If gd1+ FfC6

habe habe habe

S e b agai contoh, muatan inti efektif untuk elektron 2p

apabila orbital 1s berisi ekektron. Secara sama penetrasi orbital d dan

EMBED "Equation" \* mergeformat

dan p ( EMBED "Equation" \* mergeformat

(a) Carpenter (dibaca ke bawah

(b) Hovland (dibaca ke kanan

Struktur Atom dan Sistem Periodik Unsur.

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h\ h\ hz hE h?A( mH sH h?A( 6

4f, 5d, dan 6s

Contoh pembelahan garis spektrum dalam medan magnetik

dalam medan magnetik

Diagram energi orbital atom sebagai fungsi nomor atom

Perubahan energi ikat elektron (binding) versus nomor atom

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