Chapter 7: A Quantum Model of Atoms: Waves and Particles

Classical and Quantum Mechanics

Classical Mechanics (Newton) good for large objects, but not good from atoms, electrons, etc.
Chemistry occurs at the atomic level
Quantum Mechanics combines both wave and particle aspects of matter into a unified theory
Properties of Waves
Electromagnetic Spectrum a continuous range of radiant energy
- Radio waves, infrared radiation, visible light, ultraviolet radiation, X-rays, and gamma rays

- You should know the visible range is 400-750 nm (violet to red) and the ORDER of
Electromagnetic Radiation any form of radiant energy in the electromagnetic spectrum
Wavelength () the distance from crest to crest or trough to trough on a wave
Frequency () the number of crests of a wave that pass a stationary point of reference per second
Hertz (Hz) the SI unit of frequency, 1 Hz = 1 s-1 = 1 cycle per second (cps)
Amplitude the height of the crest or the depth of the trough of a wave WRT the centerline of the
wave
=c =2.998 108 (Speed of light in a vacuum)
- Therefore, and have a reciprocal relationship
Wave Behavior
Refraction bending of light as it passes from one medium to another of different density
Diffraction bending of electromagnetic radiation as it passes around an edge or through a narrow
opening
Interference the interaction of waves that results in either reinforcing their amplitudes
(constructive interference) or canceling them out (destructive interference)
Atomic Spectra
Fraunhofer Lines a set of dark lines in the otherwise continuous solar spectrum (because the
gaseous atoms in the outer region of the sun absorb
characteristic wavelengths)
Busen and Kirchhoff
- Atomic Emission (bright-line) Spectrum a characteristic
series of bright lines produced by excited-state atoms
- Atomic Absorption (dark-line) Spectrum a characteristic series of
dark lines produced when free, gaseous atoms are illuminated by an external source of
radiation

Each element emits characteristic electromagnetic radiation when its atoms are heated to a sufficiently high
temp
Each element absorbs characteristic electromagnetic radiation when illuminated by an external source of
radiation
These emissions and absorbs occur at the SAME

Particles of Light/Quantum Theory (a model based on energy absorbed/emitted in discrete

quantities called quanta)

Heating a Black Body/Black Body Radiation

Blackbody radiation (heated objects emit EM radiation): classical theory does not match
observations
- Infrared red red-orange orange yellow white (a little ultraviolet,
but not shorter)
Explanation: Electromagnetic radiation has particle-like properties in addition to wavelike properties
Quantum (plural quanta) the smallest discrete quantity of a particular form of energy
Quantized having values restricted to whole-number multiples of a specific base value

Photon a quantum of EM radiation (light)

hc
Energy of a single photon:
E=h=
- Units: = m, = Hz, c = m/s,
h = Js
- Plancks Constant: h=6.626 1034 J s
Photoelectric Effect - when light striking a metal surface causes e -s to be ejected (may or may not
occur)
- Threshold Frequency (0) the minimum frequency of light required to produce this effect
Intensity depends on the number of e- possible , i.e. number of photos (1 photo = 1e-)
Each photon is absorbs by an individual e-, either giving it enough to break free, or
not
If < 0, no photoelectrons (the name for e-s emitted by this effect), no matter how
intense.

If 0, number of e-s depends on intensity (more photons higher intensity)

=h 0
0, the frequency of the minimum quantum of absorbed energy needed to remove a
minimum
single e-from a metal surface minimum quantity of energy is called the metals work
needed to
KE=h h 0=h function ()
The value of is related to the strength of the attraction between the nuclei of
E photon=+ KE electron ;
the metal atoms & the e-s surrounding those nuclei (thus, different for different
E photon ,
metals)
If photons with > 0, any extra energy (in excess of ) is KE of each emitted e Hydrogen Spectrum
- Balmer lines corresponding to the visible spectrum of hydrogen fit in a simple equation
- Rydberg more general form1
1
1
2
1
=R
2 (lab)?
H
;
R H =1.097 10 nm
Only works for hydrogen
type
atoms
2

n 1 n2
- Bohr Model: hydrogen atom consists of an electron in a concentric orbit around the nucleus
Electrons can only exist in these discrete orbits
1
18
Each orbit corresponds to certain energy level

E=2.178
10
J 2
Lines in absorption and emission spectra correspond to e s moving
n between different
levels
n = 1 has the lowers energy; as n, E; zero energy means that the e- is a
free e Shows that energy is quantized because only certain values determined by n
values
The parameter n is called a quantum number
Electrons can only move between discrete orbitals (while
absorb/emitting )
Quantum Number one of four related numbers that specify the
shape and energy of orbitals in an atom; the ''address'' of an
electron in an atom or ion
Ground State the most stable, lowest energy state available to
atom or ion
Excited State any energy state in an atom or ion above the
ground state
Electron Transition movement of an electron between energy
levels
The atomic emission/absorption spectra reveal the s of e-s inside atoms
1 1 When n(final)>n(initial), is absorbed (E>0) low to high state
E=2.178 1018 2 2 When n(final)<n(initial), is emitted (E<0) high to low state
niworks for hydrogen and hydrogen-like atoms
f
nONLY
Cannot adequately explain spectra of multi-electron atoms and ions
ionization (make e- free)
Movement of electrons is different from Bohrs predictions
e- emitting energy
possible transitions for
de Broglie: matter also behaves as both a particle and a wave
hydrogen
- De Broglie wavelength: =h/mv; = m, m = kg, v = m/s
This equation tells us the wave length of all moving particles
Matter Wave the wave associated with any particle
- Electrons behave like circular wave oscillating around nucleus
Implications: the state of the electron is described by a quantum number (n)

( )

Standing Wave a wave confined to a given space (length L) where

n W

L=n (/2) ;

Isolates back and forth rather than moving through a space

Node a location in a standing wave that experiences no displacement
h
Circular standing waves account for stability of energy levels in Bohr model
x mv
Each stable wave must have circumference equal to n; C=n (min C= )
4
;
Heisenberg
Uncertainty Principle cant determine position and momentum of an e- in an atom at the
same time
Schrdinger: mathematical foundation for wave/quantum mechanics
Solutions to Schrdinger wave exn (contains both particle & wave terms) are called wave
functions ()
- Tells you what e- is doing
- A description of how the e- matter wave varies w/ location & time around the nucleus of a H
atom
Square of the wave functions | 2|= the probability of finding an electron
Orbitals defined by the | 2| ; regions around the nucleus of an atom where the probability of
finding an electron is high and identified by a unique combination of three quantum numbers
Quantum Numbers (3 of 4 must be integers) and Electron Spin
Principal quantum number ( n )
- Same as Bohrs n. As n , orbital size (i.e. the e- is more likely to be further from the
nucleus). This means that the atom becomes larger. In general as n, Energy
Angular momentum (azimuthal) quantum number ( l )
- Defines shape. Value depends on n (0 l n-1).
l is usually identified by letter ( l =0s, l =1p, l =2d, l =3f) >>>>> s, p,
d, and f orbitals
Magnetic quantum number ( m l )

Defines 3d orientation. Value depends on

(- l

ml l ).

n=1; l=0 ( s ) ; ml=0 only one 1 s orbital

n=2; l=0 ,1 ( s , p ) ; ml=0ml=1, 0 ,1 one 2 s orbital , three 2 p orbitals
n=3; l=0 ,1, 2 ( s , p , d ) ; ml =0ml =1, 0 , 1ml=2,1, 0 , 1,2 one 3 s ,three 3 p , five 3 d
n=4 ; l=0 ,1, 2,3 ( s , p , d , f ) ; ml=0 ml=3,2,1, 0 , 1,2 , 3 one 4 s , three 4 p , five 4 d , seven 4 f

Sizes

Fourth Quantum Number Spin Magnetic Quantum Number ( m s ) spin is either up or down (
)
Pauli Exclusion Principle: no 2 e-s in a multielectron atom can have the same 4 quantum numbers
- each orbital can hold two electrons
Same shell, same n
- n = 1, 1 orbital; n = 2, 4 orbitals; n = 3, 9 orbitals; n = 4, 16
orbitals
Same subshell, same n & l , same energy level
l = 0, 1 orbital; l =1, 3 orbitals; l = 2, 5 orbitals;
l =
3, 7 orbitals
There are n subshells in the nth shell
There are n2 subshells in the nth shell
There are (2 l +1) subshells in each subshell
and shapes of Atomic Orbitals
All s-orbitals are spherical
- n, orbital size, # of nodes of nodes=n=1
- Node: a region in space where the probability of finding an e- is
zero (| 2|=0 )
- To Draw: circle
A total of 3 p-orbitals, each lying along a different axis
- All have a node at the nucleolus

- To Draw: figure 8
A total of 5 d-orbitals

A total of 7 f-orbitals
The Periodic Table and Filling the Orbitals of Multi-electron Atoms
Aufbau Principle the method of building e- configurations of atoms by adding
one e- at a time as atomic number increases across the rows of the periodic table
Electron Configuration the distribution of e-s among the orbitals of an atom or
ion
Orbital Diagram depiction of the electron configuration using boxes to
represent orbitals
Core Electrons e-s in the filled, inner shells in an atom/ion that arent involved
in chemical rxns
Valence Electrons e-s in the outermost occupied shell of an atom having the
most influence on the atom's chemical behavior (reside in the valence shell)
Degenerate describes orbitals of the same energy (same n and l value)
Hund's Rule the lowest-energy electron configuration of an atom has the
maximum number of unpaired electrons, all of which have the same spin, in
degenerate orbitals
Because 4s 3d, half filled properties between ns and (n-1)d
- Three rules
Electrons always go into the lowest-energy orbital available
In general lowest to highest n, except (n-1)d & (n-2)f orbitals
Each orbital has max occupancy of two electrons (different spins)
For degenerate orbitals electrons fill each orbital singly before
paring up
Short hand: condensed electron configuration (noble gas short cut)
- Na: [Ne]3s1
- K: [Ar]4s1
- Pb:
[Xe]6s15d14f145d96p2
[Xe]4f145d106s16p2 (has to be last - )
- Ca: [Ar]4s2
- Sc:
[Ar]4s23d1
[Ar]3d14s2
- Zn: [Ar]4s23d10
- Cr: [Ar]4s13d5
- Au: [Xe]4f145d106s1
Ions
- Start with e- configuration of neutral atom.
- Then, add or remove e- to/from the outermost orbital (highest n value, and then highest
l )
- Isoelectronic describes atoms of ions that have identical electron configurations
- Elements will tend to become isoelectronic with noble gases (more stable)
- Transition metals loose first from the s orbital, not the d orbital
The Sizes of Atoms and Ions
Atomic Radius (covalent radius) half the distance btwn identical nuclear centers in a covalent
molecule
Metallic Radius half the distance between nuclear centers in the crystal of a metal
Ionic Radius radius derived from the distance between nuclear centers in ionic crystals
TREND Size
- Up to Down (n, probable r) & Left to Right (Zef) Size:
- n, probability that e- are farther away
- nuclear charge/atomic#, attractive forces , but e-, repulsive forces

 Zeff from left to right (exceptions transition metals are basically constant after the first 2)
Shielding (screening) inner-shell e-s protect outer-shell e-s from experiencing total nuclear
charge
Effective Nuclear Charge (Zeff) the attractive force toward the nucleus experienced by
an e- in an atom; the positive charge on the nucleus reduced by the extent to which
other e-s in the atom shield the e- from the nucleus (Zeff =Z-S)
- Orbital penetration: when an e- in an outer orbital has some probability of being close to the
nucleus
Orbital Penetration the probability that an electron in an outer
orbital will be as close to the nucleus as an electron in an inner shell
Penetration ability s > p> d > f 2s electrons feel a greater Zeff than
2p orbitals
- Ion
Ion size: distance between ions in an ionic compound
Depends on nuclear charge, orbitals that hold valence e -s, number of e-s
Cations: smaller than parent atom since e-s are being removed from the outermost
orbital
Anions: larger than parent atom since e-s are being added to the outermost orbital
All member of an isoelectronic species have the same number of
electrons
Increasing nuclear charge corresponds to smaller ions
- Rank the following from largest to smallest: Ar, Ca2+, Cl-, K+,
S2-

Ionization Energy (IE) the amount of needed

to
remove 1 mole of e-s from 1 mole of ground-state
atoms or ions in the gas phase
- 1st ionization energy (IE1): e.g. M(g) M+(g)
+
e- 2nd ionization energy (IE2): e.g. M+(g) M2+
(g) + e
- Trends:
with Z
exceptions
(2 to 3) shielding from s to p (Be/B and Mg.Al)
(15 to 16) half filled stability (O
vs. O+ and S vs. S+ and Se vs. Se+)
with n (because of the radius and
shielding, Zeff)
with successive ionizations
dramatic jump when finished with
valence e-s because less shielding
Electron Affinity (EA) the when 1 mole of e-s combines
with 1 mole of atoms/ions in the gas phase
- Large negative EA means that it is favorable to form the
anion
- Trends less regular
Group 1 metals increasing EA as you go down
In general, become more negative with increasing atomic number across a row
Halogens most negative
Endothermic for noble gasses, Be and Mg also slightly positive, N, too, because was
filled

Summary: Know definitions and trends

- Based on trends, be able to predict Relative sizes of atoms and ions

Relative ionization energies

Relative electron affinities
Relative properties of isoelectronic species