Sustavi

s konanim brojem
energijskih nivoa

Molekula etilena C2H4

-elektroni (suprotne projekcije spinova) (C2H4)++ ion

2 preostala elektrona (-elektroni) delokalizirani, mogu prelaziE s jednog atoma ugljika

na drugi.
126

Systems with a finite number of levels

H
C

yz plane

C
120

120
H

dva mogua stanja jednog eFig.

lektrona:
lokaliziran u blizini atoma 1 ili atoma 2
5.1. The ethylene molecule.
1

Fig. 5.2. The two possible states of a ! electron, localized near atom 1 or near atom 2.

pace
! in which the
tten provisionally
as basis vectors are "!#1 "$ !#2 "%. In this basis the Hamiltonian
However, this Hamiltonian is incomplete, because we have neglected the possibility o
written
as su energije ova dva stanja jednake. U ovoj bazi Hamiltonijan
provisionally
zbog simetrije oito
the electron
jumping from one
" to another. Within our approximations, whic
! carbon atom
moemo pisaE:
0
Emolecular
0
are those of HckelsHtheory
of
general
form of H is
!
" =most
E0 !#
$"orbitals,
H!#1$2the
0 =
1$2 "&
0 E0E0 0!
"
H0 =
$
H!#
E0 A 1$2 " = E0 !#1$2 "&
0H =E0
$
(5.2
wever, this Hamiltonian is incomplete,
because
we
have
neglected
the
possibilit
A
E0 chemistry
5.1 Elementary
quantum
electron jumping
from one is
carbon
atom tobecause
another. we
Within
approximations,
w
However,
this Hamiltonian
incomplete,
haveour
neglected
the possib
and
theovaj
off-diagonal
elementzanemaruje
A is precisely
what
gives
rise tos jtransitions
between
oblik Hamiltonijana
proces p
rijelaza
elektrona
ednog atoma
ugljika !#1
ofrugi
Hckels
theory
ofofmolecular
orbitals,
the +most
general
form
of H is
hethose
electron
jumping
from
carbon
atom
to another.
Within
A
na
suitable
openiE
ochoice
blik one
Hamiltonijana:
By
the phase
of the
basisE0vectors
we our
can approximations
take A to be rea
and
!#d2 ".
"
recf.those
of Hckels
of molecular
the which
most general
formbecause
of H is
Section
2.3.2. We theory
have written
A!
withE aorbitals,
minus
sign,
is
significant
A
0
H
=
$"
!
can be shown that A > 0.
AE0 E0A 2A
states. As we have see
If A $= 0, the states !#1 " and !#E20"Hwill
= no longer be stationary
$
E0
eigenvectors
ofprecisely
H are A
now
Ako
je A2.3.2,
0 sthe
vojstveni
vektori
Hamiltonijana:
d in
theSection
off-diagonal
element
A is
what gives
rise to transitions between
! " we can take A to be
$basisgives
#precisely
By suitable choice
of A
the1 is
phase
of thewhat
vectors
dnd!#the
element
2 ". off-diagonal
1
1 rise to transitions betwee
E

A
0
!'written
!#1 " +a !#
$
(5.3
which
+ " = A with
2 " = sign,
Section
2.3.2.
We
have
minus
is
significant
becau
1
we can take A to b
nd !#2 ". By suitable choice of the
2 phase of the basis
2 vectors
! which
"
shown2.3.2.
that AWe
> 0.have
$of a !1sign,
#A with
Fig.written
5.3.1 Energy
levels
electron.
f.beSection
a minus
is significant bec
1
!# " !#2 " =bestationary
$ states. As we have
(5.4
!'and
!#
f Abe
$= shown
0, the states
" =
2 " will 1no longer
an
that A!#>1 "0.
1
2
2
with
Section
eigenvectors
of "Hwill
are no
now
longer be stationary states. As we hav
If A $=2.3.2,
0, thethe
states
!#1 " and !#
2
! "
$
#
n Section 2.3.2, the
eigenvectors
of
H
are
now
H!"
"
=
#E

A$!"
"%
H!"
"
=
#E
+
01
+
1
01+ A$!" "&
!'+ " = !#1 " + !#2 " =
! $"
$
#

with the origin located at the center of the line. As we shall see in detail in C
0 + Aposition operator, the quantity $x!' " is the pr
if !x" is an eigenvector ofEthe
1
amplitude for finding the electron in the state !'1 " at point x. In Chapter 9 we
this probability amplitude the wave function of the electron. The squared mo
2A
nof
edijagonalni
element
at poin
E0
this probability
amplitude gives the probability
finding the
electron
uklanja degeneraciju.
called the probability density for the electron at point x. This interpretation allo
qualitatively represent the Eprobability
amplitudes " #x$ = $x!" " correspondi
0A
states !" " as in Fig. 5.4. This probability vanishes at the origin in the antis
Fig.15.3.
of symmetric
a ! electron.one !"+ ". The symmetric or antisymmetric
not
case
!"
Valne funkcije:
(x)
=Energy
but
x
in the
",
1levels

the ground-state wave function is related to the sign of A. Most of the time, grou
are
symmetric,
x svojstveni
vektor
operatora topoloaja,
which
corresponds
A > 0. pa je 1(x) = x 1 amplituda
vjerojatnosE da se elektron u stanju 1 nalazi u toki x VALNA FUNKCIJA.
H!"+ " = #E0 A$!"+ "% H!" " = #E0 + A$!" "&
(5.5)

se !" " is thestate
1(x)
2(x)
> 0,Ako
theizaberemo
symmetricda state
of lowest energy. The spectrumof
+
sredita C atoma nalaze
onian is shown in Fig. 5.3, where we see that the ground state is the state !"+ "
na osi x
spatially by studying the 1localization
E0 A$. These results can be interpreted
1
O
O
2
ron on the line joining the two carbon atoms, which we take to be the x axis,
igin located at the center of the line. As we shall see in detail in Chapter 9,
eigenvector of the position operator, the quantity $x!'1 " is the probability
Za A>0 osnovno
+
+
+
"
at
point
x.
In
Chapter
9
we
shall call
or finding
the
electron
in
the
state
!'
1
stanje je simetrino!
ility amplitude the wave function
1 of the
O electron.
2 The squared 1modulus
O of 2
(x)
ility amplitude gives the probability of +finding
the electron at point x,2also
(x)

Aproksimacija nezavisnih esEca -elektroni ne meudjeluju sa -elektronima, niE

meusobno. U ovoj aproksimaciji drugi elektron smjetamo u + stanje (-elektroni
imat e suprotne projekcije spina) energija osnovnog stanja 2(E0-A).
-2A energija delokalizacije -elektrona

to an energy lower than 6"E0 A#. Therefore, the Kkul formula does not
rrect ground-state energy. Let us begin by considering the addition of a single
ssigning the numbers 0 to 5 to the carbon atoms along the hexagonal chain
m an arbitrary origin (Fig. 5.5b).4 For example, we use !&3 " to denote the
the electron is localized near atom 3. Since it is just as easy to deal with

Molekula benzena C6H6

H
C

C
(a)

0
C
5

4 C

na ovu konguraciju
-elektrona dodajemo
jedan -elektron.

C 2
(b)

C
3

5.1 Elementary quantum ch

any number N of c
H
any number
N lanac
of carbon
atoms
an closed
we
Zatvoreni
idenEnih
atoma: forming
nsides,
eka je
sshall
tanje uuse
cha

) Hexagonal configuration of the benzenekojem
molecule.
(b) Thelokaliziran
ofu %
electrons.
je elektron
blizini
atoma
sides, we
shall
use !!skeleton
the
state
nn. = where
0" 1" # the
##
n " to denoteatom,
atom, n = 0" 1" # # # " N 1, with Nn =
forNbenzene.
6n +
. The spa
there exists a single form of orthodibromobenzene, whereas the Kkul formula predicts two different ones.
length of the bond between two carbon n
atoms
) space
is intermediate
between the
a on !! ": an
inn benzene
+N=6
N .z(1.40
The
of states
haslengths
N ofdimensions,
action
n
a
b
enzen.
) and a double (1.35 ) bond.
action
":than from 1 to 6!
oon see, it is much more convenient to number
from on
0 to 5!!
rather

H!!n " =
E0 !!n " A$!!
!!n+1 "%#
n1 "N+atoms
all
use the
symmetry
of theofproblem
under
circular
permutations
of the
of
be
the
unitary
operator
alues
and
eigenvectors
H.
Let
U
n of
+ NH.
. The
space
has operator
N
and" the
Hamiltonian
is definedofbyt
performing
circular
permutation
H!!
E0 dimensions,
!!Pn "
A$!!
+aU!!
"%#
beofthestates
unitary
rsin
Let
Ueigenvalues
n" =
n1Let
n+1
be
the
unitary
operator
to
find
the
and
eigenvectors
of
H.
P
P
d
imenzija
p
rostora
s
tanja
j
e
N
.
H
amiltonijan:
utation
of
the
atoms
in
the
direction
n

$n

1%:
ondirection
!!n ": n
We$nshall
the symmetry of the problem under circular permutat
nonthe
1%:use
ming
a circular
permutation
of the atoms in the direction n $n 1%:
"=
UP !!nof
the chain
to
the eigenvalues
and eigenvectors
H.!!
Let
shall use the symmetry
of
thefind
problem
under circular
permutations
of
the
NU""Patb
n1

1
=n "E=
A$!!
!!n+1 "%#
= !!
"" UP !!performing
" =H!!
UPn "!!
"# 1n1 " +of
(5.7) in the direction n(5
0 !!
n "n+1
!!
1
n1
n
a
circular
permutation
the
atoms
chain
eigenvectors
H.n+1
Let
!!n"#
"eigenvalues
= !!n1 "" and
U !!
!!n "of
= !!
"# UP be the unitary
(5.7) o
UPthe
U !!to"find
= !!
(5.7)
n" = U
P

n+1

According
to
(5.6)
and
(5.7),
we
can w
orming
athe
circular
permutation
of
the
atoms
in
the
direction
n

$n

1%:
Neka
j
e
U

u
nitaran
o
perator
k
oji
k
runo
p
ermuEra
a
tome
u

s
mjeru
n

(
n-1):
shall
use
symmetry
of
the
problem
under
circular
permutations
of
the
N
atoms

1
P the Hamiltonian as U !! " = !!
),ing
wetocan
write
""
U
!!
"
=
U
!!n " = !!n+
P
n
n1
n
P
(5.6)
and
(5.7),
we
can
write
the
Hamiltonian
as
P
amiltonian
as
chain to find the eigenvalues and eigenvectors
of H.
Let UP be the unitary opera

1
H =E
!!
"
=
U
!!
"
=
U
!!
"
=
!!
"#
U
!!n1 ""
P
n
n
n
n+1
P(5.7),
Pdirection
orming
aE
circular
permutation
theA$U
atoms
in %"
the can
n
$n 1%: (5.8)
%"toEof
(5.8)
According
(5.6)
and
we
write
the
Hamiltonian
as
H =
0 I A$U
P +U
P=
I

+
U
H
0
P
P
+ UP %"
(5.8)
implies
thatasH and U P commute
which
1
ording
to
(5.6)
and
(5.7),
we
can
write
the
Hamiltonian
=oemo
!! n""apisaE
U u!!
" = U H!!
!!A$U"# + U %"
(5
U !! " m
= "E=I
commute: Hamiltonijan
obliku:

n1
implies
that H andP UPn commute:
P

n+1 P

A$U
+
U
H
=
E
ording to (5.6)
(5.7),implies
we can
write
the
Hamiltonian
as(5.9)U je jednostavniji
which
U
Pcommute:
P %"vektora.
&H" Uand
Psvojstvenih
zthat
ajedniku
bazu
'0 =and
0"
(5.9)
&H"
UPH
P ' = 0" imaju
P
0"
(5.9)
operator od Hamiltonijana, pa prvo traimo njegove svojstvene
and
therefore
have
a= basis
of commo

vektore
i

s
vojstvene
v
rijednosE.
commute:
ch
implies
that
H
and
U
'
0"
&H"
U
I

A$U
+
U
%"
H
=
E
P Let us
P
erefore
have aeigenvectors.
basis of common
eigenvectors.
LetPeigenvectors
us look for
the eigenvectors (5
0look forP the
of common
and eigenvalues
of UP , as this operato
ctors.
Let
us
look
for
the
eigenvectors
i
this operator
is
a vpriori
simpler
than . H. Since UP is unitary,
genvalues
UisP ,aasopriori
UP je of
unitaran
perator
svojstvene
rijednosE
su oUblika
his operator
simpler
than
H. Since
P iseunitary,
itsP 'eigenvalues
have
exp$i(%
therefore
have
a basis
of0"common
eigenvectors.
Let
us loo
ri
than
H.and
Since
unitary,
commute:
chsimpler
implies
thatthe
H
and
Uexp$i(%
N the form
=
&H"
U
P is (see
N
P U
envalues
have
form
Section
2.3.4).
From
$U
%
=
I,
we
deduce
P
m exp$i(% (see Section
2.3.4). From $UP % = I, we deduce
N
,
as
this
operator
is
a
priori
than H
and
eigenvalues
of
U
exp$iN(%
=
1,
and
so
thes:simpler
eigenvalues
on
2.3.4).
From
$U
deduce
P
P % = I, we
(%
=
1,
and
so
the
eigenvalues
can
be
classified
by
an
integer
index
genvalues can beits
classified
by an
integer
index
s:
'
=
0"
(5
&H"
U
eigenvalues
have
the
form
exp$i(%
(see
2.3.4).
therefore
a basis
Let
usSection
look for
the From
eigenv
P
sified
by anhave
integer
indexofs: common eigenvectors.
2)
2)s
exp$iN(%
=
1,
and
so
the
eigenvalues
can
be
classified
by
an
integ
,
as
this
operator
is
a
priori
simpler
than
H.
Since
U
is
u
eigenvalues
of
U
N
s
vojstvenih
v
rijednosE

2)s
=
(
=
(
P= ( =
P
"
s
=
0"
1"
#
#
#
"
N

1#
(5.10)
(
s
s of
therefore
have
a=basis
eigenvectors. Let us
look for
"
s
0"
1"
# # #common
"exp$i(%
(5.10)
=
=
(
N
operatora
UP. the
N eigenvect
NN 1# (see
s
eigenvalues
have
the
form
Section
2.3.4).
From
$U
%
=
I,
we
1" # # # " NN 1#
(5.10)
P
2)s

a space ofNeigenvector
dimension N
eigenvectors are orthogonal and form a ba
normalized
!*N,s1
"the
in corresponding
the form
1
!
!
2 eigenvector
of !*
!s ". =
Let130
uscwrite
a
normalized
in the
form
number
of levels
!!
""
!c
!
=
1#Systems with!*as "finite
(5.11)
n
n
n
pripadni
n
ormirani
s
vojstveni
v
ektori:
N
1
N
1
!
!
n=0
n=0
2
130
Systems
with a (5.11)
finite number of levels
!*
"
=
c
!!
""
!c
!
=
1#!! with
s
n
n
n
N
1
N
1
130 Equating the coefficients
Systems
a
finite
number
of
levels
of
"
in
these
two
equations
leads to
! n
!
2
n=0
n=0
!* " =
cn !!n ""
!cn ! = 1#
(5.1
ve
Equating thes coefficients
of
!!
"
in
these
two
equations
leads
to
n equations in"
i"two
n=0
s n=0
s number
Equating
the
coefficients
of
!!
"
in
these
130
Systems
withcwith
a number
finite
of levels
c
=
e
c
ealeads
c0 #ofto
130
Systems
finite
number
of levels
n
130
Systems
with
levels
have
n+1
n aorfinite
n =
N
1
N
1
!
!
i"s
in"s
UP !*
cn !!we
" = N 1cn+1 !!n ""
On
the
one Nhand
c
=
e
c
cleads
i"s
in"
s" =
n1 have
1
s or cn = e
n+1
n
0#
!
!
c
=
e
c
or
c
=
e
c
#
Equating
the
coefficients
of
!!
"
in
these
two
equations
to t
The
corresponding
tonthe
exp$i"
is to leads
Equating
the coefficients
of !!
" inof
these
equations
leads
Equating
!!n "ntwo
in these
equations
n+1
neigenvalue
0two
n
s % then
n=0 eigenvector
n=0the coefficients
UP !*s " =
cn !!n1 " =
cn+1 !!
n ""
N
1
N
1
!
!
n=0
n=0
The
eigenvector
corresponding
to
the
exp$i"
then is
N
1
i"eigenvalue
in"ss% in"
s !!
i"
in"
i"
UP !*s " = to cthe
!!
"
=
c
""
The eigenvector corresponding
eigenvalue
exp$i"
%
then
is
!
s
s
1
s
c
=
e
c
or
c
=
e
c
n
n1
n+1
ns
c!&n+1
=
e
c
or
e
c
#
in"
c
=
e
or
=
e
n+1
n c
0 # s c0 #
sncnc=
n
0
n+1
n
n
!!n "#
s " = n=0 e
n=0
N
1
N
1
N1n=0
! i(
!
N
1
i(s
in"s
!
s
1 to
U
!*
"
=
e
!*
"
=
e
c
!!
"#
in"
!&
"
=
e

The
eigenvector
corresponding
the
eigenvalue
exp$i"
then
is
N
1
P
s
s
n
n
s
s
n "# s % is
The
eigenvector
corresponding
to
the
eigenvalue
exp$i"
%!!then
The
eigenvector
corresponding
to
the
eigenvalue
exp$i"
%
then
while on the other
!
!&
"
=
e
!!
"#

s
s
s
n
i(
N n=0 The bases !! " and
UP !*The
ei(s !*s " c=0n=0
cn !!
= 1/e s N
ensures
that N!&
"
is
normalized.
n=0
s " = choice
n "#
s
n
N
1
!
N
1
n=0
1

! N!
1 3.1.2. Taking into
i(s definition 1
i(s N
1in"#Section
complementary
according
to ethe
given
!
in"
U
!*
"
=
!*
"
=
e
c
!!
1
s in"
P c s = 1/ N s ensures
n
n" in"
s normalized.
The
choice
that
!&
is
The
base!
!&
"
=
e
!!ns "#
0
s
!&
"
=
e
!!
"#

s
The
normiranje:
choice
c
=
1/
N
ensures
that
!&
"
is
normalized.
The
bases
!!
"
and
"
=
e
!!
"#

ss n=0 E!&
n
0
n
the expression
(5.8) for H, the eigenvalue
is
given
by
n
s s
N n=0
N
N
complementary
according
to
the
definition
given
in
Section
n=0
complementary according to the definition
given #in Sectionn=0
3.1.2. Taking3.1.2.
into T
"

expression
(5.8)
for
H,ethe
E
given
by
i"sE eigenvalue
s
s is
the expressionthe
(5.8)
for H,Ethe
eigenvalue
isi"given
by

=
E
=
E

A
+
e
2A
cos
"
s
s
0
0
s
The
choice
c0 =
ensures
that
"!&is" normalized.
TheThe
bas
The choice
cchoice
that
!&
is!&snormalized.
The
bases
!!
The
c0N1/
=ensures
1/N" N
ensures
that
is
normalized.
0 = 1/
s"
#
"
s
# i"
i"
complementary
according
to
the
definition
given
s
i"
i"
complementary
according
to
the
definition
ins cos
Section
3.1.2.
svojstvene
vrijednosE
Hamiltonijana:
sA definition
="in
Es 0 Section

cos3.1.2
"Taki
complementary
to
the
given
in2A
Section
s 3
Es = E0according
=e given
E0+e2A
A E
e s s=+E
e0
or (Fig.
5.6)

thethe
expression
H,eigenvalue
the the
eigenvalue
given
by by
s is
the expression
(5.8) (5.8)
for(5.8)
H,for
the
Es is E
given
by
expression
for
H,
eigenvalue
E
is
given
s
2's
" cos # # #
Es = E
or (Fig. 5.6) or (Fig. 5.6)
"0 2A
#
"s N i"s
i"
i"A
i"
E
=
E0
=
E

e
+
e
2A cos "s
s
s
i"
i"
Es = E0s
+A
e 2's
2A
EsA=0 eE0
=cos
E0 "
e s=
+E
e 0 s2's
s 2A cos

s=3

2's
#
Es = E0 2A cos
N

E0 + 2A

(5.13)
s=4

s=2

E0 + A
5.13)
directly
without
the intermediary
of the circular permuUmjesto
direktne
dijagonalizacije

rvo dijagonaliziramo
er, Hamiltonijana,
our use of UPpillustrates
a general strategy and is not just a / 3
operator
simetrije as
koji itkomuEra
sometimes greatly,
hallunitarni
often use
this strategy,
simplifies,
/3
s Hamiltonijanom.
Hamiltonian: instead of diagonalizing H directly, we first diagetryStanja
operators
commute
H, when such operators / 3
s i = Nwhich
-s imaju
jednake ewith
nergije.
E0 A
etry
of the
5.1 sElementary
Osim
s=0 iphysical
s=N-1 (N problem.
paran), stanja
u
s = 5quantum chemistry
s=1
degenerirana.
he dvostruko
values s and
s = N s give the same value of the energy;
vektori the
Hamiltonijana
sof
realnim
realdegenerate.
possible
to even),
obtain
eigenvectors
H
components
Svojstveni
1 (for N
energy levels
arewith
doubly
It isby forming linear combinati

koecijenEma:
of !!
s " and !!s ":

s=0

E0 2A

N
1
E Fig. 5.6. Energy2levels
"
1
2$ns
of a '
electron of the benzene mole
s = 3 !!s+ " = "!!s " + !!s "# =
!%n "&
cos
(5
E0 + 2A
N n=0
N
2
! N 1
2 "
2$ns
s1= 2

E0s "
+
A !!s "# =
sin
(5
!!s " = "!!
!%n "'
N n=0
N
i 2
/3

Now we can write / 3down the results for the eigenvalues of H and the correspond

s = 1& s = 5 E = E0 A
Benzen +(N=6): 1 s#= 01 E 1= E0 2A
1 1$
!!1 " = 1& & & 1& & &
21 2
2 2
!!3" = "1& 1& 1& 1& 1& 1#(

$
# 1 1
1
1
!!1 " = 0& & & 0& & (
2 2
2 2

s = 2& s = 4 6E = E0 + A
s#= 1& s = 5 E = E0 A$
$
# 1 1
1
1
1
1
1
1
1

!!2+ " = + 1& 1 &# 1& 1&

1 & 1& 1 $!!2 " = 0& &# 1& 0&1 & 1 ( 1 $
2 & &
2 0&2 & &20& 2 & (
!!13" = 2 1&2 & &21&
!!1 " =
3

s = s = 3 E = E0 + 2A

2 2

s = 2& s = 4 E = E0 + A
1
#
1
1
1$
1 1&
!!3 " = + "1& 1&
1&11& 1#'
!!26" = 1& & & 1& & &
2
2
2
2
3

2 2

!!2 "

$
# 1
1
1
1(5.16
= 0& & & 0& & (
2
2
2
2

Let us now find the

is, the state of lowest energy of the benzen
s =ground
s = 3 state,
E = Ethat
0 + 2A
molecule, by placing the1 six delocalized $ electrons. In the approximation where th
!!3 " = "1&
1&
1& 1&
1&be
1#'
electrons are independent,
this
state
will
obtained by first putting two electrons o
6
opposite spins in the level E0 2A. The Pauli principle (Chapter 13) forbids any mo
Energija
tanja the
: 2 elektrona
suprotnih
spina uof najniem
tanju energije
Letosnovnog
us now sfind
ground state,
thatprojekcija
is, the state
lowest senergy
of the b
electrons
in
this
level.
As
the
level
"E

A#
is
doubly
degenerate,
we
can
0 degenerirano pa moe sadravaE 2 para put fou
(E0-2A).
S
lijedee
s
tanje
(
E
-A)
j
e
d
vostruko
0
molecule, by placing the six delocalized $ electrons. In the approximation whe
electrons
in itsuprotnih
(two pairs
of electrons
with
opposite
spins).
elektrona
spinova
energija
osnovnog
stanja
je: This gives the total energy

electrons are independent, this state will be obtained by first putting two electr
opposite spins in
the2"E
levelE2A#
2A.
ThePauli
(Chapter 13) forbids(5.17
any
0 +
E=
4"E
A# =principle
6E0 8A'
0
0
electrons in this level. As the level "E0 A# is doubly degenerate, we can pu

in the present section, the ammonia molecule in Section 5.3, and the two-level atom
5.2.1
A spin 1/2
in a periodic
a periodic
magnetic
field magnetic field
Section5.2.1
5.4. A spin 1/2 in
5.2.1
A spin
a fact
periodic
magnetic
field
magnetic
resonance
(NMR)
rests
on
the fact
that anwith
atomic
nucleus with non
ic Nuclear
resonance
(NMR)
rests1/2
onin
the
that
an
atomic
nucleus
nonzero
13
spin resonance
possesses
a(NMR)
magnetic
moment.
We
limit
ourselves
to(1spin-1/2
nuclei (1 H,
agnetic
magnetic
moment.
We shall
limit
ourselves
spin-1/2
nuclei
H,
C,
rests
on the
fact shall
thattoan
atomic
nucleus
with
nonzero
19
5.2.1
Awhich
spin 1/2
in operator
a periodic
magnetic
field
etc.),
for moment.
which
theWe
magnetic
moment,
which
is spin-1/2
an operator
in quantum
hichaF,the
magnetic
moment,
an
into
quantum
mechanics,
ses
magnetic
shall islimit
ourselves
nuclei
(1 H, 13 C,mecha
given
by magnetic
Nuclear
magnetic
resonance
(NMR)
rests is
onan
theoperator
fact thatin
anquantum
atomic nucleus
with nonze
or iswhich
the
moment,
which
mechanics,
Spin 1/2 ua pmagnetic
eriodinom
magnetskom
polju
1 ourselves to spin-1/2 nuclei (1 H, 13
1
spin possesses
moment.
We
shall
limit
% = % S% = %!&"
%
(5
$
% = % S% = %!&"
%$
(5.18)
19
2 is an operator in quantum mechanic
2 moment,
F, etc.), for which the magnetic
which
1
1H, 13C, 19F, ...)
%

j
ezgre
s
pina

0

i
maju
m
agnetski
m
oment.
P
romatramo
j
ezgre
s
pina
1
/2
(
$
%
=
%
S
=
%!
&"
%
(5.18)
is
given
by
%
spin
operator
3.2 2andin%Section
is the
gyromagnetic
ratio:
where
S is defined
the spin in
operator
3.2 and photons
% is the
gyromagnetic
ratio:
78Sectiondefined
Polarization:
and
spin-1/ 2 particles
1
qp $
%
qisp &"
%
=
%
S
=
%!
%the gyromagnetic ratio:
(5.1
the spin operator defined
in
Section
3.2
and
%
%=%
'
(5.19)
% = %2
'
(5
z
2mp
2m
p
qp
%
where
Sgis
the spin13 operator
3.2
and % is the gyromagnetic
ratio:
=19% 13in Section
'
(5.19)
iromagnetski
faktor: %defined
19
e proton,
1.40
C, 5.261.40
for for
F,2m
and
so on. The nuclear spin is placed
% = 5!59
forfor
the proton,
C,
p 5.26 for F, and so on. The nuclear spin is pl
qp
%a0 magnetic
B can write
%13Oz
pointing field
in theB
direction.
Following
(3.61),
we
the we can write
ield
pointing
in
the
Oz
direction.
Following
(3.61),
in B
%
=
%
'
(5.1
0
19
orofthethe
proton,
1.40
for
C,
5.26
for
F,
and
so
on.
The
nuclear
spin
is
placed
2m
p
nuclear
vanjsko m
agnetsko
olje B0 uspin
smjeru
spin
s
ofasthe pnuclear
as Oz
Hamiltonian
H
0
% 0 pointing in the Oz direction.
Following
(3.61), we can
write the
tic field B

19
% = 5!59 for the proton, 1.40
F,
and
so
on.
The
nuclear
spin is plac
1 for 13 C, 5.261 for
1
1
%
as %!B
n H ofHthe
!#%!B
$
% B0%spin
= H
&z B
%=0
0 =nuclear
0$
0 &z "0 &z = !#0 &z "(5.20)
=

%
=

0
pointing
in
the
Oz
direction.
Following
(3.61), we can write (5
t
in a 0magnetic
field B
2
2 2
0
2
y
1 which
1
thethe
nuclear
spin
as
Hamiltonian
H
0 of in
orwith
in matrix
form
basis
in
&
is
diagonal:
%matrix
z basis
%!B
!#which
$
%in B
in
(5.20)
#0 =H%B
orLarmorova
form
in0 &
the
frekvencija
0 =
0 =
z =
0 &z " &z is diagonal:
0,
t
x 1
"1 ! 2
! 2
"
1 0 = #$
% 0 0= 1 %!B#
!#0 &z " (5.21)
H
%
&
=

(5.2
0B
0
0 0is
z diagonal:
!
= in! the basis in which
H0 form
%B0 , or in matrix
&
z
2
2

Nuklearna magnetska rezonanca (NMR)

0 in
0
Ifthe
theproton
vectors
$+%since
$%of
are
represented
as
column
vectors
rix
form
basis
in the
which
&
isZeeman
diagonal:
We
that
the
proton
charge
qin
isamagnetic
positive
is no
m
Wethe
note
that
since
charge
qand
is positive
is
no
sign
inthere
the
definiti
have
a two-level
system,
the
two
a 0there
spin
1/2
magnetic
field,
wi
pminus
z note
plevels
ve
a
two-level
system,
two
Zeeman
levels
of
a
spin
1/2
in
a
field,
with
!
frequency,
the, in
frequency
with
which
thecontrast
classical
magnetic
moment
precesses
about
B0
! 0for
a
periodic
radiofrequency
field
Now
let
us
add
to
the
constant
field
B
!
"
!
"
of
!
,
in
to
the
case
of
Section
3.2.5
for
the
electron
"
!
of
!
contrast
to
the
case
of
Section
3.2.5
the
electron.
Here
!
is
the
Larm
0
0
0
the energy
difference
of the
levels
being
!!
energy
difference
of
the
levels
being
!!
. 0 . precession is in 1the clockwise
0
1
6
0
0
#
(Fig. 3.7).
In
the
case
of
the
proton
the
Larmor
direction.
0
to
the
xOy
plane
and
rotating
in
the
clockwise
direction,
that
is,
in about
the
sa
frequency,
the
frequency
with
which
the
classical
magnetic
frequency,
the
frequency
with
which
the
classical$+%
magnetic
moment
precesses
=
# $%
=
# mo
!
!

s
vojstveni
v
ektori:
!
(5.21)
=

!
H
a
periodic
radiofrequency
field
B
"t#
parall
Now
let
us
add
to
the
constant
field
B
!
!
0
1 therefore
a0 periodic
radiofrequency
field
B1 "t#
Now
us "+#
add
to the
field
B0 the
0is
1 paralle
/2,3.7).
and
"#
has!:
energy
!!
We
The let
state
has
energy
!!
0theconstant
#
23.7).
0the
0 /2.
(Fig.
Inangular
thestate
case speed
of precession
the
proton
the
Larmor
precession
is in
0 of
(Fig.
In
case
proton
the
Larmor
in
the
clockwise
directio
as
the
Larmor
precession,
with
6
6
to
the
xOy
plane
and
rotating
in
the
clockwise
direction,
that
is,
in
the
same
directio
the
xOy
plane
and"+#
rotating
intwo
the
clockwise
direction,
that
is,
the
same
direction
have
a two-level
the
Zeeman
levels
ofstate
a spin
1/2
in
ainmagnetic
field,
with
/2,
and
the
state
ene
The
state
"+#(normalized)
has
energy
!!
energije:
and
the
"#
energy
!!
/2."#
Wehas
therefo
The state system,
hasthe
energy
!!
0has
most
general
state
vector
$%%

can
be
wri
0 /2,
0!
as
the
Larmor
precession,
with
angular
speed
!:
! 1Zeeman
the
precession,
with
angular
speed
B
"t#0!:
=
Blevels
cos
. Zeeman
y 1/2
sin !t#$
theLarmor
energy
the
levels
being
!!
. system,
have
atwo
the
of a spin
have
a two-level
system,
the
of
atwo
in levels
a magnetic
field,
w"
1 "
!1/2
Razlika
edifference
nergija
dva of
nivoa
spina
1/2
utwo-level
m
agnetskom
pxolju
je !t
spin
0
&
! 1 "t# parallel
!difference
the
energy
the
levels
being !!
. B
a periodic
radiofrequency
field
Now let
add difference
to the constant
field
B
the us
energy
of
the
levels
being
!!$%%
.ofy=
0or
!
0 cos
0
B
"t#
=
B
"
x
!t

sin
!t#$
(5.2
!
&$+%
+
'$%
$%%
=
1=B
B ad1odamo
"t#
"
x1be
cos
!t

ythe
sinconstant
!t#$
(5.22
practice,
such
field
can
obtained
by
of
two
coils
placed
1olje
6means
!
xOy
kIn
onstantnom
p
olju
B
p
B
(t)
p
aralelno
r
avnini
x
Oy
k
oje
r
oEra
u

s
mjeru
!
!
a
periodic
radiofreq
Now
let
us
add
to
field
B
'a
to the
plane
and
rotating
in
the
clockwise
direction,
that
is,
in
the
same
direction
field B1 "t# paral
Now let us add to
0 the constant field
1 B0 a periodic radiofrequency
0
6
Larmorove
precesije
kutnom
bby
rzinom
the
: plane
6frequency
and
Oy
axes
and
fed
anxOy
alternating
current
ofthe
!.
The contri
to
the
and
rotating
in
clockwise
direction,
In
practice,
such
a
field
can
be
obtained
by
means
of
two
coils
placed
along
the
O
to
the
xOy
plane
and
rotating
in
clockwise
direction,
that
is,
in
the
same
directi
as
the
Larmor
precession,
with
angular
speed
!:
practice, such a field can
bevectors
obtained
by
means
ofbetwo
coils
placed along
thethat
Ox
The
$+%
and
$%
can
used
to
construct
a
Hermitian
o
!
Hamiltonian
due
to
the
field
B
"t#
is
as
the
Larmor
precession,
with
angular
speed
!:
the and
Larmor
with angular
speed
!:
1current
axes
by
an
alternating
of
frequency!.!.The
Thecontribution
contributiontotothth
d and
Oy Oy
axesas
and
fed fed
by precession,
anvectors
alternating
current
of
frequency
with
eigenvalues
!/2: (5.22)
are
eigenvectors
of
S
!
B!1 "t# = B1 "x cos !t y sinz !t#$
Hamiltonian
to the
field
B1 "t#
! 1 "t#
miltonian
duedue
to the
field
B
is B!is1 "t# =!B1 "x cos !t1 y B!sin
"t#
= B1 "x cos !t y sin !t#$(5.2
!t#$
# = !!11"&
$ !t1#&y sin !t#'
$ 1
! B11 "t#
cos
H1 "t# = %
x
In practice, such a field can be obtained
means
two coils=placed
along
the=Ox!
2of
1by
!
$+%#+$

$%#$
!
"
S
=

"
1
z
+

In
practice,
such
a
field
can
be
obtained
by
means
of
two
cO
!
practice,
such
a
field
can
be
obtained
by
means
of
two
coils
placed
along
the
!!
"t#
=

%
!

B
"t#
=

"&
cos
!t

&
sin
!t#'
H
2
2
2
1
1
1
x
y
and Oy In
axes
and
fed
by
an
alternating
current
of
frequency
!.
The
contribution
to
the
! B1 "t# = !!
cos !t &y sin !t#'
H1 "t# = %
1 "&
x often
2
=
(B
is
the
Rabi
frequency,
called
the!.current
nutation
where
!
and
Oy
axes
and
fed
by of
anfrequency
alternating
of frequency
frequencyto !t!
2
1
1
and
Oy
axes
and
fed
by
an
alternating
current
The
contribution
!
Hamiltonian due to the field B1 "t# is
!matrix
Hamiltonian
due
toprojectors
the
field
B
"t# the
is form
"
arecalled
statesis$+%
and
$%.
W
where
"+ Hamiltonian
The
total
time-dependent
H"t#
in
then
!and
1on

=
(B
is
the
Rabi
frequency,
often
the
nutation
frequency
in
NMR
where
!
Hamiltonian
due
to
the
field
B
"t#
is
1
1
1
nut
Rabi
frequency, often called the nutation
frequency
!!
in
NMR
ere !1 = (B1 is the
Rabi
frekvencija
nut
1
#
,
the
z
component
of
the
spin,
we
associate
a
Hermitian
3.2
Spin
1/2
85
!
" opera
z
time-dependent
H"t#
in
matrix
form
isthen
then
1
! 1 "t# H"t#
i!t
= Hamiltonian
%
! B
=
"&
cos
!t

&
sin
!t#'
H1 "t#Hamiltonian
e The
totaltotal
time-dependent
in!!
matrix
form
is
1
! 1 y"t#!=0 !!
1H "t#
x =1
!called

%
! $%
B
!t &y
!
11e"&x cos
1
2
!!
"t#
=

%
!

B
"t#
=

"&
cos
&y sin
!t#'
H
of
states
!
.
The
vectors
$+%
and
also
eigenstate
ukupni Hamiltonijan: 1 H"t# = H01 + H1!
1
x ! !t are
"t#
=

'
!
"
2
i!t
"
2 matrices:
i!t
The matrices !x , !y , and !z are called the 1Pauli
!
e
!
2
i!t
!
!
e
1
0
0
1
is
diagonal.
In
this
basis
S
is
represented
by
basis
in
which
S
1
!
!
e
z
z
is the
Rabi
frequency,
often
called
the
nutation
frequency
!
in
NMR.
where !1 = (B1 H"t#
0
1
!
+
H
"t#
=

H"t#
=
H
'
(5.2
nut
(B
is
the
Rabi
frequency,
often
called
the
nutation
where
!
1 =1 !1often called
i!t
H1 "t#frequency,
Hthe
'frequency !nut in(5.23
the nutation
NMs
where !1 = (B=
0 +0Rabi
i!t
1 is
!
e
!
2
The
physical
property
corresponding
to
the
z
component
of
the
1
0
!
!
!
"
"
"
!
e
!
2
The total
time-dependent
Hamiltonian
H"t#
in
matrix
form
is
then
1
0 H"t#
total
time-dependent
Hamiltonian
is th
&0y . in
It matrix
is nowform
easy
t
where
wetime-dependent
have used
the
expressions
(3.49)
for form
&x and
The total
Hamiltonian
in
matrix
is
0 1 The
0H"t#
i
1 then
+!/2
if the "state
$%%
$+%
or $%.(3.47)
!x =thevalue
=!/2for
=
# to
" in!or
!&zvector
!
" is"easy
!the
ymatrix
the
Schrdinger
equation
form
(4.13),
decomposing
state
and
.
It
is
now
writevecto
dow
where
we
have
used
expressions
(3.49)
&
i!t
!
1
0
i
0
0
1
x
y
It1is
to
write
down
ere we have used the expressions (3.49) for
1 &x1 and
1
!0 &y!. !
e !now
!
!
i!t easy
0
1e
e
!
+
H
"t#
=

H"t#
=
H
!
+
H
"t#
=

H"t#
=
H
'
(5.23)
0
1 state vector ")"t##
1 the
0 and
the basis
vectors
"+#
the Schrdinger
equation
in
matrix
form
(4.13),
on
+H
decomposing
H"t#
=form
H1 0"#:
' !1")"t##
(5.2
e i!t onto
!
1 "t#
Schrdinger
equation
in matrix
(4.13),
the
state 2vector
!! e i!t 0 i!t
!
2= decomposing

!e

0 !

2
1
0
the
Schrdinger
equation
in
matrix
form
(4.13),
decomposing
the
state
vector
")"t#o
chrdinger equation in matrix form (4.13),Postulate
decomposing
state
vector
")"t##
IV: thethe
evolution
equation
thevectors
basis
"+#v"#:
and expressions

vremenski
ektor
s"#:
tanja moemo (3.49)
razviE ufor
bazi
, }:
&y . It is now easy to wr
where
we vectors
have
used
the
&{x+ and
sis
"+#ovisan
and
The time evolution of the state vector !!"t#"
of a quantum system
the Schrdinger equation in matrix form (4.13), decomposing the state vector ")
")"t## = c+ "t#"+# + c "t#"#$
evolution equation
(5
")"t##
the basis vectors "+# and "#:= c+ "t#"+# + c "t#"#$
d!!"t#" for c "t#:
WeSchrdingerova
obtain the following
system
of edifferential
equations
j
ednadba
v
remenske
volucije:
H"t#!!"t#" $
i!
btain the following system of ")"t##
differential
equations
c= "t#:
+ cdtfor
"t#"#$
= c+ "t#"+#
1
1
dc
i!t
=

!
!
c

e
c $
i
1
1
dc
0
1

diferencijalna
jednadba system
za koecijente
razvoja:
i!t
We
obtain
the following
of
differential
equations
for c "t#:
dt
2
2
= operator
!0 cH"t#
!1called
is
e cthe
(5
i
The Hermitian
$ Hamiltonian.
dt
2
2
Let us be precise
on
the
conditions
which Eq. (4.11) applies.
1
1 under
dc
=
!1 ei!tbecunderstood
$
i
quantum system,
and
this !
statement
as follows:
0 c should
dt 5.2.2 Rabi
2 oscillations
2
under consideration must not be part of a larger quantum system, a
5.2.2 Rabi oscillations
at length
in Chapterequations
15. However,
is validthe
if coefficients
the quantum (sys
To solve the system
of differential
(5.25),(4.11)
we define

Rabi
o
scilacije
lve the system of classical
differential
equations
(5.25),that
weit define
the coefficients
"t#v
system,
which means
is not necessarily
isolated.(Itis
5.2.2
Rabi
oscillations
i!0 t/2
c
"t#
=
(
"t#
e
$

the case of a spin 1/2 submitted

to
a
time-dependent
magnetic field (
deniramo koecijente: c "t# = ( "t# ei!0 t/2 $
(5
To solve the system
of differential
equations
(5.25), we
define the coefficients
two-level
atom submitted
to a classical
electromagnetic
field
(Sectio
! 1 = 0 the
This definition has an interesting geometrical interpretation. When B
but not for an atom interacting with
a quantized electromagnetic
! 1 = direction
!
i!0 B
t/2
definition
has
an
interesting
geometrical
interpretation.
When
B
0 the
simply
performs
Larmor
precession
(Fig.
3.7)
about
in
the
clockwise
0
c
"t#
=
(
"t#
e
$
Kada je B1=0, spin In
precesira
L
armorovom
f
rekvencijom
o
ko
B

u

s
mjeru
k
azaljke
n
a
s
atu.

the latter case, the time evolution

of0 the state vector (or more ac
! 0 in
y performs
(Fig.
B
the clockwise
w
Uvodimo rLarmor
eferentni precession
sustav koji roEra
oko 3.7)
osi Oz about
Larmorovom
frekvencijom
0 vdirection
alna
operator)
of the atom is not governed by a Hamiltonian. A !Hamilto
funkcija
u novom has
sustavu:
This
definition
an
interesting
geometrical interpretation. When B1 = 0
6
!
We could also use a field
B1 "t#
to Ox; +
seefield
Exercise
5.5.6.
only
forparallel
the atom
system.
! 0 in the clockwise direc
simply performs
Larmor
precession
(Fig.
3.7)
about
B
! 1 "t# parallel
The operator
H has the
dimensions of energy, and we do identify H
uld also use a field B
to Ox; see Exercise
5.5.6.

!"#t$"
!" !"
#t$"#t$":
=e
becomes
!0 , in which !"#t$"
#
7

i!0 t/2
i!0 t/2
!"#t$"
=
c
#t$
e
!+"
+
c
#t$
e
!"&
+

ch !"#t$" becomes
!"
#t$":
the components
state vector
the coefficients ( #t$ are just i!
! ofi!the
"in the ro
i!t
0 t/2
#
i!
%zet/2 0 t/2 !+" +
1
1
dc
0
=
c
#t$
c
#t$
e
!"&
(5.27)
1
!0
!1 e
i!t
#t$" = e +
!"#t$"the transformation

i!
t/2c $ of interpreting
= !frame.
!
c # !"#t$"
Another
e!"
(5.25)
(5.27) is to note
0 %zway

anglei!t
' about Oz is 'exp#
2
2
!i!10eis
!0 /2$, so that
2about
i!0 t/2
t/2
The operator
which
performs
a
rotation
by
an
angle
'
Oz
exp#i'%
=
c
#t$
e
!+"
+
c
#t$
e
!"&
#t$
are
just
the
components
of
the
state
the ro
thethen
coefficients
(
i!
t/2
i!
t/2
z in(5.27)
+
= c+ #t$e 0 !+"
+ c #t$ e 0 !"&
(5.27) vector
#t$
areused
just
the
components
of(3.49)
the
state
vector
in &
the.(5.27)
rotating
reference
the coefficients
(Another
i!
0 t/2
frame.
way
of
interpreting
the
transformation
is
to
note
and
It
is
now
easy
t
where
we
have
the
expressions
for
&
c
#t$
=
e
c
#0$
(
#t$
=
const&
x
y
The
operator
which
performs
a
rotation
by
angle
'
about
Oz
is
/2$,
so
that
an/2)

exp#i'%
Operator
r
otacije
z
a
k
ut

o
ko
o
si
z

j
e
e
xp(-i

(t)
s
u
k
omponente
v
ektora
s
tanja

z
&
or
whichAnother
performsway
a rotation
by an anglethe
' about
z Oz is exp#i'%

frame.
of interpreting
transformation
(5.27)
is so
to that
note that if B1 = 0,
z /2$,
then
the
Schrdinger
equation
in
matrix
form
(4.13),
decomposing
the state
vecto
u
s
ustavu
k
oji
r
oEra.
A
ko
j
e
B
=0

Rabi
oscillations
#t$components
are just1 theofcomponents
of the
staterotating
vectorreference
in the rotating
reference
the5.2.2
coefficients
(

#t$
are
just
the
the
state
vector
in
the
ients
(
then
and the transformation (5.26) allows
us to eliminate the trivial time
dep
&
i!0 t/2
the
basis
vectors
"+#
and
"#:
frame.
Another
way
of
interpreting
the
transformation
(5.27)
is
to
note
that
if
B
=
0,
&#t$
other
of interpreting
thewe
transformation
that
if
0,const&
1
= e is to note
c(#0$
(
1 ==
#t$(5.27)
B
i!c0the
t/2
entialway
equations
(5.25),
define
coefficients
"t#
as
H
.
Using
c #t$ = e
c #0$ ( #t$ = const&
0
then
!
"
"t#"+#
+
c
"t#"#$
")"t##
=
c
dcallows
+us1 to eliminate
d(the i!
and
the
transformation
(5.26)
trivial
time
dep
i!
i!
t/2

i!00t/2
0 t/2
0 t/2
c
#t$
=
e
c
#0$
(
#t$
=
const&
and cthe
transformation
(5.26)
allows
us
to
eliminate
the
trivial
time
dependence
due
to
c
#t$
=
e
c
#0$
(
#t$
=
const&
"t#
=
(
"t#
e
$
(5.26)
=

!
i
(
+
i
)
e

0
dt
2
dt
H0 . Using
H0 . Using
We
obtainallows
the following
system
of
differential
equations
for
!! time"
" dependence
nsformation
(5.26)
us to eliminate
the
trivial
dependence
due
to c "t#: due to
and
the
transformation
(5.26)
allows
us
to
eliminate
the
trivial
time
!
esting geometrical
interpretation.
When
B1d(=
the spin
1 0 i!
dc
d( i!0 t/2
1
dc
we
can
transform
(5.25)
into

t/2
0
H0 . Using
!0 (
)
= the
iclockwise
!0(=+ i
) i!te
e +1iwith
1direction
dc
!dt
! iB
"
cession
(Fig.
3.7)
about
in
!
"
0
2!0 c !dt
Iz jednadbe zdc
a koecijente
razvoja: d(i2 dti!=t/2 dt
c $
1 dc
1e
1
1
d(
1
d(
0

$t 0 t/2
= i!0 ( +
i
i
) 2i#!!
e( +
2#t$
=
!dt
) = !1 ei*t ( #t$&
e0i!
i
=
(
0 !1i e
dt
2
dt

we can transform
intodt(5.25)
we can (5.25)
transform
2
dt
dt into
2
2
to Ox; see
Exercise
nsform
(5.25)
into5.5.6.d(
1 frequency
we can transform
(5.25)
$
of
external(5.28)
field
The difference
#!

!
into*1=
i#!!
$t between the
i*t
1 the i*t
d(
0
01

i#!!
i
= i !1 e = !
( #t$
=

(
#t$&
0 $t !1 e
! e
e and
(offset
(NMR
Rabithe
oscillations
1 dti#!!
1 5.2.2
d( frequency
1i*t
#t$ =frequency
1
#t$& pr
2
is
called
the
detuning,
by
0 $t2
i
= !d(
#t$ i#!!
= 02!
( #t$&1
(5.28)
2
1(dt
1e
$t 1 e
i*t
dt
2
2
i
=

!
!
e
(
#t$
=

e
(
#t$&
(5.28)
1solvethe
in the of
1 of
field and
$
between
frequency
the
external
the
Larmor
The difference
*=
#!

!
particularly
easy
to
(5.28)
case
resonance,
*
=
0
(we
shal
ToThe
solve
the
system
of
differential
equations
(5.25),
we
define
the
coefficie
0
dt * =2 #! ! $ between the2 frequency of the external field
difference
0anjskog

razlika
rekvencije
polja
i Lfield
armorove
frekvencije.
thefterminology):
frequency
theoffset
external
andby
the
Larmor
ence
* = #!
!called
0 $ between
frequency
isreason
the
detuning,
andvof
the
frequency
NMR
practitioners. It is
for
this
$
between
the
frequency
of
the
external
field
andbytheNMR
Larmor
The
difference
*
=
#!

!
i!
t/2
frequency
is
called
the
detuning,
and
the
offset
frequency
0
isparticularly
called the easy
detuning,
and
the
offset
frequency
by
NMR
practitioners.
It
is
0
= ( "t#*e= 0 (we
$ shall see shortly pra
to solve (5.28) in the case cof "t#
resonance,
the
frequency
is
called
the
detuning,
and
the
offset
frequency
by
NMR
practitioners.
It
is
d(
1
y easy to solve
(5.28) in the
case
resonance,
= 0the
(wecase
see
shortly the * = 0 (we shall
easy
toofsolve
(5.28)* in
resonance,
shallof
reason forparticularly
this terminology):
=
!01(we
i
( #t$&
particularly
easy
to
solve
(5.28)
in
the
case
of
resonance,
*
=
shall see When
shortly the
this
terminology):
! =
This definition has an interesting geometrical
B
dt
2 interpretation.

dt

operator
performs
by !an
H"t#
#t$" = ewhich
1
= H0 +aHrotation
!"#t$"The
0!"
!"#t$"
1 "t# =

dt case 2of
easysee
to shortly
solve (5.28
particularly easy to solve (5.28) in d(
the
= 0 (we shall
the
1 resonance, *particularly

!1to(time
i with=respect
#t$& andreason
(5.29)
for second
this terminology):
Differentiating
one of the equations
using
the
equation,
reason
for this terminology):
dt
2
Sluaj
rezonance: = 0.
we
obtain

1
Differentiating one of the equations2d(with
respect
to time and using the second equation,
id ( = 1 !2 1 ( #t$&
(5.29)
!
=

(
#t$&
(5.30)
dt
2
we obtain
1
2
dt
4
Differentiating
one ofequation,
the equa
d2 (with
1 resonance
Differentiating one of the5.2
equations
respect
time(NMR)
and
using the second
Nuclear
magnetic
135

2 to
This equation can be integrated immediately.
The
solution
depends
on
two
constants
a
!
=

(
#t$&
(5.30)
1
2
we obtain
we
obtain
2
2
dt
4
and b, !a! + !b! = 1, which are related to the initial conditions:
rotating the spin by an angle ! about
Ox1 axis. This can be seen using the expression
d2 (the
$ The
# ! t $ depends on two
#
2
This
equation
can
be
integrated
immediately.
solution
constants
a
!1tan
!
=
(
#t$&
(5.30)
1 about the Ox axis:8
forRjeenja:
the operator
that
performs
a
rotation
by
angle
!

1
2
(+ #t$
b sin conditions:
adtcos
5.2) Nuclear magnetic resonance (NMR
4+initial
and b, !a!2 + !b!2 = 1, which
are=related
to2 the
2
(5.31)
! solution
# t $$ The
##!" t $This
$
equation
can
be
integrate
This equation can be integrated immediately.
depends
on
two
constants
!
rotating#!
the
spin
by
an
angle
!
about
the
Ox
axis.
This
canabe
!
!
11 t
11 t
initial
ibbicos
& ) b, !a!2 + !b!2 = 1, which ar
#t$
=
ia
sin to=the
&conditions:
U
exp
((+#t$
sin
=related
cos
xa#!$%
x 2 ' and
and b, !a!2 + !b!2 = 1, which
are"!
5.2
Nuclear
magnetic
for
the operator
thatresonance
performs
rotation by an angle ! abou
22 +
2
2 a(NMR)
(5.31)
#!
$$
##! t $$ geometrical
#
"
!
t
Equation (5.31) can be given a very interesting
interpretation
in
the
rotating
!11 t
1!1 t
!
(
+
b
sin
)
#t$
=
a
cos
rotating
the
spin
by
an
angle
!
about
the
Ox
axis.
This
can
be
seen
using
the
expre
(+ #t$
(+#t$' =
t oib
cos
&
ia
sin za 2kasut !
Wereference
then have
&
U
"!
#!$%
=
exp
i
Deniramo
kut =
t. Oangle
perator
risotacije

ko
o
si
O
z:
frame.
If 1the
defined
=
',
the
operation
(5.31)
amounts
to
22
x
x '
1
2
8 (5.31)
2
for the operator that performs a rotation
the Ox axis:
# ! tby
$#an angle
# !!
$ about
$
t
!
!
!
"
"
" in the rotating
1
1
!
!
Equation (5.31)( can
be
given
a
very
interesting
geometrical
interpretation
(

ib
cos
&
#t$
=
ia
sin
i
sin
cos
( #t$
/2
#t$
#0$
a
(
"
!
2
2
i!&
+
+
7
We
then
have
x
2
2
Another method of solving (5.25)
frame rotating
frequency
) amounts
(5.32)to
=angle
eis to use' aisreference
= ! with
!the !.operation
reference
frame.
If
the
defined
as
t
=
',
(5.31)
!
!
1
( #t$
ib" #
'!
&xinterpretation
U("!#0$
exp
i sin"2i cos
x #!$%
! =geometrical
2
!given a
Equation (5.31)can be given a veryinteresting
the
Equation
(5.31)
can
berotating
2 i!& /2 (+ #0$ in
i sin
cos
(+ #t$
2
x
e reference
= Ifamounts
reference frame. If the angle ' is defined as !
= ',=the
operation
(5.31)
to '!
frame.
the
!angle
1 t#t$
#0$
(
(
7
i
sin
cos

Another
method
of
solving
(5.25)
is
to
use
a
reference
frame
rotating
with
frequency
!.
sluaju rezonance
=0
u sustavu
koji picture
roEra spin
idi protation
olje B1 u sismjeru
x (u ovom
in U
agreement
with (5.31).
The
classical
of vthe
alsoOinteresting.
2 In 2
We
then have
B1 n
e ovisi the
o vremenu).
" 1 , which is aligned along
thesustavu
rotating
frame,
spin sees a time-independent field B
$!
#
7
in agreement
with with
(5.31).
The
picture
of
theis rotat
7
!
"
"
"
Another method of!
solving (5.25)
is to use a reference
frame rotating
frequency
!.classical
!
!
Another
method
of
solving
(5.25)
to use
"
Ox. Thus (5.31) is( nothing
other the
thanrotating
the
Larmor
precession
about
B
with
an
angular
i
sin
cos
1
#t$
#0$
a
(
"
2 sees a time-independent
2
frame, othe
spin
field B
i!&x /2
+
+

L
armorova
p
recesija
ko
B

f
rekvencijom

.
)
=
e
=
1 !at time t! = 0 the
1 spin is in the (
frequency *1 . To illustrate
this
rotation,
let
us
suppose
that
( #t$
( #0$
ib precession
Ox. Thus
(5.31) is nothing
than the Larmor
i sin 2othercos
2
state #+$, which has the lowest energy !* /2: a = 1) b = 0. At time t the probability

a!+ +" = #+$+% = 1# a! " = #$% = 1# a!+ 2" = #$+% = 0$ (3.33)

" 1 , which is aligned
the rotating
frame,
the
spin sees
a time-independent
field
B
in
agreement
with
(5.31).
The
classical
picture
of
the
rotation
is
also
interesting.
In In
inPretpostavimo
agreement
with
(5.31).
Thet=0
classical
picture
of
the
rotation
is
also
interesting.
We
then
have
"
d
a
j
e
u

t
renutku
s
pin
u

s
tanju

+
k
oje
i
ma
e
nergiju
/2

Ox.
Thus
(5.31)
is
nothing
other
than the
Larmor
about
Balong
If the
vectors
$+%
and $%
are
represented
as column
vectors
0
" 1 ,precession
1 with an an
which
is
aligned
the
rotating
frame,
the
spin
sees
a
time-independent
field
B
"
, which
aligned
the rotating
frame, the
spinillustrate
sees
a"this
time-independent
field B1that
$time
!isan
!Larmor!let
"!
" "us#suppose
"0 the along
*1!. To
rotation,
t
=
spin is
!
!atwith
"
Ox. Thus frequency
(5.31) is nothing
other
than
the
precession
about
B
angular
i
sin
cos
1
1
0
(
#t$
#0$
a
(
"
2
2 B with an angular
/2the Larmor
+
Ox. Thus state
(5.31)#+$,
is nothing
other
precession
about
(5.32
= than
e i!&#x=
=
which+$+%
has
the
lowest
energy
=
1)
b
= 0.1 At time
the proba
=
$%
= !*
#0 /2:at atime
(3.34)
frequency *1 . To
illustrate
this
rotation,
let
us
suppose
that
t
=
0
is
in)tthe
!
! the spin
#t$
#0$
(
(
ib
0
1
i
sin
cos

frequency p*1 .of

Tofinding
illustrate this
rotation,
let us
at2 time 2t = 0 the spin is in the
spinenergy
in the !*
state
#$suppose
will
bebthat

state #+$, which

has the the
lowest
/2:
a
=
1)
=
0.
At time t the probability
0
#+$,
which
has the lowest
energy$%%
!*
a=
b = 0.
At time t the probability
thestate
general
vector
!
can
be 1)
written
0 /2:
pmost
oftrenutku
finding
the
in with
thestate
state
#$The
will
be
% * ist &also interesting. In
in (normalized)
agreement
(5.31).
classical
picture
of
theas
rotation
u

t je spin
vjerojatnost
nalaenja
spina
u stanju

+
i
li

:

1
2
2
2
p of finding the spin in the state
#$
will
be
!+ #t$#
" = cos"
p+spin
) is aligned along
#t$
=sees
#%+#+#t$$#
= #(
,
which
the rotating frame, the
a time-independent
field
B
&% * t &
1 2
= &$+%
+ '$%
$%%
$%
1
2
2 Larmor
2 precession
" 1 (3.35)
&
Ox. Thus $%%
(5.31)
is #%+#+#t$$#
nothing
other
than
the
about
B
with an angula(
&
%
p+ #t$
)
=
= or
#(+ #t$#
==cos'
*
t
*
t
1
2
2 2
2
222 1
p #t$this
= #%#+#t$$#
==
#(cos
#t$#
= sin
)
#%+#+#t$$#
= #(+let
#t$#
frequency *p1+. #t$
To =
illustrate
rotation,
us
suppose
that
at
time
t ='0 the(5.33)
spin is in the
% * t &2
2
The vectors $+%
and#+$,
$%which
can behas
used
construct
a Hermitian
operator
thatt these
11) b =S0.
2 energy
2
z such
state
the to
lowest
!*
At time
the probability
(5.33)
p #t$ =
'
#%#+#t$$#
= #( #t$#
=0 /2:
sin2a =%
&
1t
22 *
eigenvalues
vectors are eigenvectors
of
2 #$
2
z with
p of
finding
the
spin
in the
will
be
The
oscillations
between
thestate
two
levels
are
called
Rabi
pS#t$
' oscillations. A spin wh
=
#%#+#t$$#
=!/2:
#(
#t$#
=
sin

2 at times
!
"& t given by
initially
in
the
state
#+$
will
be
found
in
the
state
#$
#
$
#
$
%0* A
The oscillations
between the two levels1are called Rabi 1oscillations.
spin which is
1
1
1t
2 "
2
2
Oscilacije
izzmeu
s$+%#+$
tanja +
i$%#$
:
R
abi
o
scilacije.

!

=
!
"
!
S
=
=

#
(3.36)
) A spin
=in#%+#+#t$$#
=#(at+Rabi
#t$#
=
cos
+ #$
+ #t$levels
!
"
initially
in the2state
#+$ willthe
be p
found
the
state
times
t
given
by
The
oscillations
between
two
are
called
oscillations.
which is
0
1
2
2
*1 t 2
1
(5.33(
&
%2)
=
n
+
,)
n
=
0)
1)
3)
'
'
'
initially
in
the
state
#+$
will
be
found
in
the
state
#$
at
times
t
given
by
*
t
!
"
1
2
2u stanju
2 s vjerojatnou 1 u vremenima:
Spin "koji
se poetno nalazi
+,
n
ai $+%
e se 2and
2=
p #t$
' property
#%#+#t$$#
= #(
= sin
on
the
$%.
With
the physical
where
*u1 t stanju
1states
#t$#
+ and " are projectors
2
= !
n+
n = 0) 1) 2) 3) ' ' '
(5.34)
",)a Hermitian
#z , the z component of the spin,
we
associate
operator
S
acting
in
the
space
2
2
z
*1 t
1
"
If
the
radiofrequency
field
B
#t$ ,)
islevels
applied
during
aoftime
interval
satisfying
=
n
+
neigenstates
=
1) 2) 3)
' S' 'z ,oscillations.
Thevectors
oscillations
between
thealso
are0)
called
Rabi
At%spin
which (i
1two
and
they "0)
form
the (5.34)
of states ! . The
$+% and
$% are
called
2 that a , pulse has been applied. When
ininitially
with
n2B
=#t$
0, isitbasis
is said
"
in
the
state
#+$
will
be
in athe
state
at "0)
times
tmatrix
given by
is
diagonal.
In
this
Szfound
is
represented
by#$
a diagonal
(3.36).
basis
Sgeneral
If in
thewhich
radiofrequency
field
applied
during
time
interval
t% satisfying
(5.34),
z
1
Kad
se radiofrekventno
Bthat
(t)
p
rimjenjuje
u""
ibeen
ntervalu
[spin
0,t]: takes
1the
t=
-PULS
!
Theinphysical
property
to
the
z
component
of
the
well-defined
1
general
with n =corresponding
0, it ispolje
said
a
,
pulse
has
applied.
When
!
"
t
*
If the radiofrequency field B #t$ is
during
*11applied
11 ,a time interval "0) t% satisfying (5.34),
value +!/2 or !/2 if the state 1vector
$%%
is
$+%
$%.) n =
=
n
+
n=
1) 3)
2)'3)
n
+
,)
0) 0)
1) 2)
''''')
(5.34(
! that
" , pulse2or
in Kad
general
n = 0, it*is
said
a
has
been
applied.
When
2
2
2
2
se B1with
(t) primjenjuje
u

i
ntervalu
[
0,t]:

/2-PULS,
s
pin
k
oji
s
e
p
oetno

t=/2
1 ,
1
1t
= n+
) n = 0) 1) 2) 3)nalazio
' ' ' ) u stanju + (5.35)
linearna
2
2
2
!
"
we
sayradiofrequency
that a ,/2
has
The spin
is then
in a+
linear
combination
"11been
*1 t pulse
kombinacija
i t%.

If the
field
B
#t$ ,
is applied.
applied during
a time
interval
"0)
satisfying
(5.34)

utions
of which
seek
ininform
the
form
136
Systems
with a finite number of levels
of
which
we we
seek
in
the
eions
solutions
of
which
we
seek
the
form
In
the
off-resonance
case,
starting
from
differenti
the solutions of which we seek in the form (5.28) we obtain
!+ "t#a =second-order
ei$ t %
36 U openitom
Systems
with afinite
number
of levels
equation
(+ :sluaju
t
ad nema
rezonance
0

d
iferencijalna
jednadba 2. reda za
i$the
t i$

theforsolutions
of kwhich
we
seek
in
form
i$i$
t %t
!
"t#
=
e

!
"t#
=
e
%
!++!"t#"t#==e e % %
+
mber koecijente:
of levels
The
values
$
are
theofroots
+
Systems
with of
a
finite
levelsof a second-order equation given
number
2 in the
he solutions of which we 2seek
form
1 ei$ t %
d (+ 2 2i 2d(
1/2
+"t#
!
=
+
'
#
by
frequency
$
=
"&
+
+ equation
*1 (given
- equation
0)
alues
of
$are
second-order
equation
given
asaa function
afunction
function
of
of values
$of
the the
roots
ofroots
aofsecond-order
as a as
function
of the
1 second-order
ees
values
theroots
roots
of2aofa
of
the
+ =given
$
The
ofare
are
the
asecond-order
equation
given
as
of(5.3
the
$are
seek
ions
of which
we
in
the
form
*
dt
*
dt
2
1
1
2 2 2 2 1/222 1/2
i$ t
2 1/2
2by
1/2
+
'
#
by
yncy
$
=
"&
+
'
#
$
=
"&
1
!
"t#
=
e
%
+
'
#
by
quency
$
=
"&
+
'
#
by
frequency
$
=
"&
1
1
+
1 1of $ are the roots of a second-order
The
values
equation
given
as a functio

('

$)%
$
=
t

i$
t
% Traimo
1/2 =
2
1 e 11 %1
rjeenje
obliku:
by
frequency
$u=
"&21 + '!2+#"t#
(5.37)
$ 3.3.6,
=
('

(5.37)
=
('
$)%
$)%
$('
= $)%
The
values of $ are
the roots
of
a(3.67),
second-order
equation
given
as a function
('
$)%
(5o
$$
=
8

This expression is derived

from Exercise
eq.
by
taking
the
unit
vector
p

parallel
to
Ox.
2 !+ is
2the 22for
The
solution
ofof(5.36)
linear as
combination
of
exp"i$
1 a given
er
equation
given
as
a
function
2
2
1/2
+ t#
ues
of
$
are
the
roots
of
a
second-order
equation
a
function
of
the
Def. $ = "&1 + ' #
by
requency
$ = (' $)%
2
2
1/2
The
solution
of
(5.36)
for
!
is
a
linear
combination
ofexp"i$
exp"i$
t#t#
and
exp"i$
ey solution
of
for
is
linear
combination
of
and
exp"i$
tion
(5.36)
for
!+by
is
linear
combination
of 2exp"i$
exp"i$
t#:
+a alinear
t#: t#:
+ '(5.36)
# for
$ of
= "&
++t#

olution
of 1(5.36)
!+!a+is
combination
of
exp"i$
and
exp"i$
+ t# and

1!+ "t# = * exp"i$++t# + + exp"i$ t#%

$)%
$a linear
= t#('+combination
The solution of (5.36)
for=!
is
of exp"i$+ t# and exp"i$(
1
+ exp"i$
!
"t#
*
+
exp"i$
t#%
$)%
(5.37)
!
"t#
=
*
exp"i$
t#
+
+
exp"i$
t#%
+exp"i$
+2

!+ "t#
=+ *$
exp"i$
++
('
+
$)%
(5.37)
+ t#
t#% t#%
= *=exp"i$
t#
+ + exp"i$
+ "t#
+
Let !us
choose
the
initial
conditions
!
"0#
= 0. Since
"0#
=
1,
!
+

2
!
"t#
=
*combination
exp"i$
t# +=of
+0.exp"i$
+linear
+"0#
!t#%
The
of
(5.36)
for
!
is
a
exp"i$
t#
and
++"0#,
Let
us
choose
the
initial
conditions
!
Since
"0#
!!
"0#, these
these
"0#
=
1,
!
initial
conditions
are
equivalent
to
+

exp"i$
thoose
ussolution
choose
the
initial
conditions
!
"0#
=
0.
Since
!
"0#

"0#
=
1,
!
+
+
t#:
tion
of
exp"i$
t#
and
exp"i$
t#:
Izaberemo
p
oetne
u
vjete:
+

the
initial
conditions
!
"0#
=
0.
Since
!
"0#

!
"0#,
these
"0#
=
1,
!
exp"i$
ution
of conditions
(5.36)
for are
!+ conditions
is
a linear+ combination
+ "0#, th
choose
the initial
!+ "0# =1,of!exp"i$
0. and
Since
! "0#
+ t#
+t#: !
"0# =
initial
equivalent
to
tial
conditions
are
equivalent
to
Letareusequivalent
choose thetoinitial
1, ! "0# = 0. Since ! "0# ! + "0
nditions
conditions
!+to
"t# conditions
= * exp"i$!++*"0#
t#+
+=
exp"i$
++=
1 and t#%
*$+ + +$ = 0,
+
exp"i$ t#%are equivalent
!
"t#
=
*
exp"i$
t#
+
+
exp"i$
t#%
initial conditions
are*equivalent
to *$+ ++$ = 0,
+
+1 and
+=
+=
*
+
+
1
and
*$
+ + +$
= 0,
*
+
+
=
1
and
*$
+
+$
=
0,
+

=
0. vSince
!and
!++ "0#,
! "0#
rijedi:
so
*+conditions
= 1 these
and
*$=
+
+$
0,0. Since ! "0# ! + "0#,
Let
usBudui
choose
theconditions
initial
!+!"0#
"0#
1,0.
!Since
"0#
+=
==!
hoose
the
initial
!
"0#
! "0#, these
"0#
=
1,
*
+
+
=
1
and
*$
+
+$
+

"0#
and so
+
= 0, +
d so conditions are equivalent to
$
$+
nitial
onditions
are equivalent to
, +=
%
$
$*+=
$
$
*
=

,
+
=
%
$
$
+
+ +$ and
= 0,so
*$
=$ $, $
+ += $$
%
*
+
+
=
1
and
*$
+
+$
= 0,
*
=

,
+
=
%
*++
= 1result
and can
*$$
+written
+$$
=
0,+ $

+$
+
=

+
The
final
be
as
*
=

,
+
%
%
The final result can be written as$ $* = $ , $ + =
$
"
!$
e final result can be written as
i't/2

* =$

, + =2
%
!+ "t# =
2
$
$
"
!
$
i't/2
$t
e
$t
Konano rjeenje moe se !napisaE
bliku:
1 i't/2
(5.38)
"t# as
= u oi&
$ cos $t
+
The final result can be written
i&
! "t# = $ e
, sin 2 ,
sin2 i'
1 (
!
e
"t#
=
$!
2

"
i't/2
$
$t
ei&1 i't/2 $t
$t
!

i'
sin
,
(5.38
"t#
=
$
cos
!
,
(5.39)
== 0. eThe factor
sin exp"i't/2#
+ "t# '
which reduces to (5.31) when
arises
because
'
is
the
L
2which
2 to (5.31) when ' = 0. The
$
reduces
2
frequency in the rotating reference frame. Equation
(5.39)
is rotating
particularly
interesti
frequency
in
the
reference
fram
i&
$t
which reduces to (5.31) when ' = 0.1The
factor exp"i't/2# arises because ' is the Larmor
i't/2
e #+$sin
(5.39
= state
shows that if we start !from
at tshows
=, 0, the
probability
of
finding
the
s
"t# the
that
if
we
start
from
the
state
$ frame. Equation
2
frequency in the rotating reference
(5.39) is particularly interesting. #+
It
theshows
statethat
#$ifatwetime
t from
is the state #+$ at t =the
stateprobability
#$ at time
tfinding
is
start
0,
the
of
in
which reduces to (5.31) when ' = 0. The factor2 exp"i't/2#
arises because ' isthe
the spin
Larmo
#
$
Ako state
je sistem
stanju +, vjerojatnost
da se u trenutku
t nalazi u stanju :
the
#$ patoetno
time tu is
$t
&
2
1
frequency in the rotating reference
(5.39)
is particularly interesting.
I(
pframe.
%
"t# = 2Equation
sin
p
"t#
=
#
$

2
$
2
&
shows that if we start from the state
#+$
at
of finding the spin
1 t =20, $t
p "t# = 2 sin the probability
%
(5.40)i
$
2
the state #$ at time t is
We see
that the maximum
We see that the maximum probability of making
a$ transition
from the probability
state #+$
#
2
$t
&resonance
m#$
aksimum
vjerojatnosE
rijelaza
iz sby
tanja
making
+ u state
stanje
zfor
a: of
$t/2
We
see
that
the
maximum
probability
of
a transition
from
#+$ tobythea
#$
=the
-/2
is given
state
for $t/2
= -/2pis
given
a
curve
width
':state
p "t# = 12 sin2
%
(5.40
state #$ for $t/2 = -/2 is given by a $
resonance curve
of
width
':
2
2
2
2
&21
max
&
&
&
1
max
p = 2 = (
2 1
2
pmax
= &21 12 = of&2making
=
%
&
We see that the maximum
a
transition
from
the
state #+$
to th
probability
1
1
$ (5.41)
&
2
2
2
p = $2 = &
=
%
+
'
&
+
"&

&
#
0
2 1 2
2 1
2
$ by a&resonance
&1curve
+ "& of
&width
state #$ for $t/2 = -/2 is given
':
0#
1 +'
As shown in Fig. 5.7, the Rabi oscillatio
Rezonantna
AsAsshown
in
Fig.
5.7,
the
Rabi
oscillations
are
maximal
atkrivulja
resonance
and decrease
ra
2
2 are maximal
2 resonance
shown in Fig. 5.7, the Rabi &
oscillations
at
and
decrease
rapidly
&1
&1 with growing '. This has a
in amplitude
1
max
p
=
=
=
%
(5.41
ininamplitude
with
growing
'.
This
has
a
clear
intuitive
interpretation:
the
influence
'. This
amplitude with growing
has
a
intuitive
interpretation:
the
influence
of
the
2 clear
2
2
2
2
%
$
&1 + ' radiofrequency
&1 + "& &0 # (RF) field B1 is maxima
% 1 isismaximal
%B
radiofrequency
maximalwhen
when
it rotates
with
same
the
radiofrequency (RF)
(RF) field
field B
it
rotates
withLarmor
the the
same
speedspeed
as about
theasspin
1
undergoing
precession
O
%
%
As
shown in Larmor
Fig.
5.7, precession
the Rabi oscillations
are
maximal
at
resonance
and decrease
rapidl
undergoing
Larmor
precession
about
thethe
spin
sees
a constant
field field
B1 instead
undergoing
aboutOz,
Oz,so
sothat
that
spin
sees
a constant
B1 in

5.2 Nuclear magnetic resonance (NMR)

p (t)

p (t)

=0

= 31

Rabi oscilacije su maksimalne (p_max =1) u sluaju rezonance i brzo slabe u amplitudi s
5.7. porastom
Rabi oscillations.
(a) ! = 0, (b) ! = 3"1 . In case (b) the maximum value of p #t$
.
utjecaj radiofrekventnog (RF) polja B1 je najvei kada roEra jednakom kutnom brzinom
kojom spin precesira oko smjera Oz (Larmorova precesija oko polja B0) u tom sluaju
5.2.3
spin vidi konstantno polje
B1. Principles of NMR and MRI

R is principally used to determine the structure of molecules in chemistry or bi

for studying condensed matter in the solid or liquid state. A detailed desc
ow NMR works would take us too far afield, and so we shall only touch
" 0 of several
subject. The sample under study is placed in a uniform field B

Molekula amonijaka
NH3 QM sustav s dva nivoa

1
dvije konguracije molekule koja
roEra oko osi simetrije. Simetrija na
reeksiju s obzirom na ravninu koju
tvore atomi vodika energije 1
i 2 su jednake.
2

Ukupni Hamiltonijan:

Molekula NH3 u elektrinom polju: maser

dipolni moment d okomit na ravninu vodikovih
atoma
molekula NH3 u elektrinom polju u smjeru Oz
energija klasinog dipola u elektrinom polju:

QM: dipolnom momentu pridruujemo perator D. Reprezentacija dipolnog operatora u

bazi {1 , 2 }:

ukupni Hamiltonijan molekule NH3 u elektrinom polju :

1) StaEko elektrino polje svojstvene vrijednosE:

i) ako je d >> A energije su E0 d i pripadni priblini svojstveni vektori 1 i 2

ii) slabo polje d << A

svojstveni vektori su + i do na 2.

2) Pretpostavimo da elektrino polje ima oscilatornu vremensku ovisnost:

Vektori baze: stacionarna stanja + i . U ovoj je bazi matrica Hamiltonijana:

OpeniE vektor stanja:

Iz jednadbe evolucije u vremenu:

Kada je

Redeniramo skalu energije:

 za 0 0

elektrino polje inducira prijelaze iz stanja + u i obratno.

AproksimaEvno rjeenje kada je perturbacija uzrokovana vanjskim poljem slaba:

Rabi frekvencija:
1 << 0 aproksimacija slabog vanjskog polja.
Rezonanca 0
brze oscilacije, usrednjen po
vremenu, efekat ovih lanova je
mali.

Pretpostavke za analiEko aproksimaEvno rjeenje: 1 << 0 i << 0 .

Za rezonantnu frekvenciju = 0 ako pretpostavimo da je u trenutku t=0 molekula u
stanju energije E0+A:

Molekula prelazi iz stanja u stanje + kutnom frekvencijom 1/2 = d0/2

sEmulirana emisija.
Ako su molekule poetno u stanju + sEmulirana apsorpcija kvanta EM polja u
prijelazu u stanje .
Ako se molekule mogu dovesE u poetno pobueno stanje (inverzija zaposjednua),
sEmulirana emisija moe se upotrijebiE za pojaavanje EM polja (maser).

Ne-rezonantni prijelazi

Neka je u trenutku t=0 molekula u stanju + vjerojatnost da u trenutku t molekula bude

u stanju :

Rabi frekvencija.

AproksimaEvno rjeenje za:

Poetni uvjet za t=0
U procesu apsorpcije elektromagnetskog zraenja sistem prelazi iz osnovnog u pobueno
stanje. Ako je 1t << 1 + 1, u kratkom intervalu ne mijenja se puno od t=0 vrijednosE.

vjerojatnost prijelaza:
Omjer s vjerojatnou prijelaza u rezonanci:

Upotrijebimo:
f(0;t) je priblino -funkcija:

Vjerojatnost prijelaza molekule iz stanja + u stanje apsorpcijom e.m. zraenja:

Fluks EM polja odreen je PoynEng vektorom:

Frekvencija elektrinog polja nije egzaktna spektar frekvencija irine . Neka je ()

intenzitet polja po jedinici frekvencije integrirana vjerojatnost prijelaza:

vjerojatnost prijelaza po jedinici vremena:

Atom s dva nivoa

Aproksimacija atoma s dva nivoa: g osnovno stanje, e pobueno stanje. Prijelazi
izmeu ovih stanja EeEg = 0, inducirani EM poljem frekvencije 0.
elektrni dipolni prijelazi odreeni su matrini elemenEma dipolnog operatora D.
Vrijedi uvjet 1 << 0, za Rabi frekvenciju 1 = d0/.
poluklasian opis: atom promatramo kao kvantni sistem, ali je EM polje klasino.

Spontana emisija SEmulirana emisija Apsorpcija

Promatramo skup atoma koji imaju dva nivoa E1 i E2 (E1 < E2) i nalaze se u upljini na
temperaturi T. upljina sadri i polje zraenja gustoe energije (Planckov zakon):

N ukupan broj atoma. N1(2)(t) broj atoma u stanju energije E1(2)

A(): broj prijelaza E1 E2 u jedinici vremena (sEmulirana apsorpcija)

B(): broj prijelaza E2 E1 u jedinici vremena (sEmulirana emisija)
U stanju termodinamike ravnotee:


Omjer zaposjednua Boltzmann zakon:

 moramo jo ukljuiE lan koji opisuje spontanu emisiju (ne ovisi o ()):

u ravnotenom stanju dN1/dt = 0

usporedba s Planckovim zakonom zraenja

Intenzitet zraenja:
Za vjerojatnost dipolnog prijelaza po jedinici vremena dobili smo:

2
1
d
J ()
p(t) = 4 2
J
()
=
A()
=
A
t
40 2 c
c

vjerojatnost sEmulirane emisije

vjerojatnost spontane emisije