LECTURE NOTE

by Prof. Kook Joe Shin

Professor Emeritus, Seoul National University
Chair Professor, UNIST

Textbook: D. W. Oxtoby, H. P. Gillis, and A. Campion,

“Principles of Modern Chemistry”, 7th ed., Cengage, (2012)

Chapter 05
Quantum Mechanics
and Atomic Structure

1
 Hydrogen Atom
➢ Energy
Levels
● Schrödinger equation for the hydrogen atom
(or one-electron atoms) exactly solvable !

Reduced mass: =
m1m2/(m1+m2)
● Energy
values

2
➢ Quantum numbers for hydrogen
atom
● Principal quantum number, n = 1, 2, 3, …
~ Energy of hydrogen atom depends only on n

● (Orbital) Angular momentum quantum number,

l = 0, 1, 2, …, n – 1
●
…
Magnetic quantum number,
ml = – l, – l +1, …, 0, …, l – 1, l
• Angular momentum, L

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There are n2 sets of quantum numbers (n, l, ml).
Each set identifies a specific quantum state of the atom.
n2 – fold degeneracy
More than one state for an energy level:
n = 1 (l = 0, m = 0)
n = 2 (l = 0, m = 0),
(l = 1, m = 1), (l = 1, m = 0), (l = 1, m = – 1)
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● Conventional labeling of states
l=0 s, l = 1 p, l = 2 d, l = 3 f
sharp principal diffuse fundamental

1s: (n = 1, l = 0), 2s: (n = 2, l = 0), 2p: (n = 2, l = 1)

➢ Wave
Functions
…
For each quantum state (n, l, ml), the wave function is given by

“Orbital”

Rnl (r) ~ radial part

~ angular part, “spherical harmonics”

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➢ s-orbitals ,
Spherically symmetric, independent of angles

Fig. 5.5. H1s R100(r) Fig. 5.6. (a) H1s [R100(r)]2, probability density
orbital. and (b) its 3D representation with varying
intensity of a color.
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Fig. 5.7. (a) Plot of an electron probability density of a hydrogen atom in its 1s,
2s, and 3s states. Plots of (b) the wave functions and (c) the probability density
given by the square of the wave functions vs. distance from the nucleus. 7
Fig. 5.8. (a) Contour plots of H1s, H2s, H3s orbitals.
(b) Radial wave functions. (c) Radial probability density.
➢ p-
orbitals
(l=1, m = –1, 0, 1) Y1–1 ( , ), Y10 ( , ), Y11 ( ,
)

Fig. 5.9. (a) The angular wave function and (b) its square
of the hydrogen pz orbital. (red: + value, blue: – value)
Fig. 5.10. Radial wave functions Rnl for np orbitals and the corresponding
radial probability densities r2Rnl2.
 Zero probability at r = 0 for all wave functions with l > 0
• Electrons with angular momentum are moving around
the nucleus, not toward it, and cannot “penetrate” toward
the nucleus.
Radial part of np-orbital, Rnl n–2 radial nodes

➢ d-orbitals
…
(l = 2, m = –2, –1 , 0, 1, 2)
3d–2, 3d–1, 3d0, 3d1, 3d2 3dxy, 3dyz, 3dxz,
,
Each d-orbital has two angular nodes.
Radial part of nd-orbital, Rn2, has n–3 nodes.
Total # of nodes is n–1.
Fig. 5.13. Shapes of five 3d-orbitals
Fig. 5.14. Radial probability density for hydrogen orbitals. Small arrows
show the average distance of the electron from the nucleus
➢ Electron
Spin

Otto Stern Walther Gerlach

(DE,1888-1969) (DE,1889-1979)
Nobel Prize in Physics (1943)

● Stern-Gerlach experiment (1921)

Rotating charged particle (electron) behaves like a magnet
interacts with the applied field
● Space quantization
Beam of H (originally with Ag) atoms travelling through
a nonuniform magnetic field deflects into two bands

Fig. 5.15. The Stern-Gerlach experiment. A beam of hydrogen atoms

is split into two beams when it traverses a non-uniform magnetic field.
➢ Spin angular momentum, S
~ Pure quantum mechanical property

For an electron in H (or Ag) atom, s = 1/2.

● Spin quantum number, ms fourth quantum number!

ms = +1/2 ( -electron, denoted as ) or

ms = –1/2 ( -electron, denoted as )
 Shell Model for Many-Electron Atoms
➢ Hatree
Orbitals

Douglas Hartree Vladimir Fock

(UK,1897-1958) (RUS,1898-1974)
● Hartree-Fock theory
~ Self-consistent field (SCF) orbital approximation
method for many electron atoms
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● Three basic assumptions in Hartree-Fock Theory
(1) Each electron moves in an effective field due to all
the other electrons.
(2) Effective field of an electron i is obtained by
averaging
its Coulomb interactions with other electrons.
(3) Effective field is spherically symmetric.

• Each electron is described by a one-electron orbital.

• Simultaneous equations for the unknown effective

field and the unknown one-electron orbitals.
Self-consistent solution by iteration

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Fig. 5.16. Dependence of radial probability distribution densities on
distance from the nucleus for Hartree orbitals in argon with n = 1, 2, 3.
Fig. 5.17. The radial charge density in the argon atom as calculated by Hartree’s
method. The charge is arrayed into three shells corresponding to n = 1, 2, 3.
Fig. 5.18. Approximate energy-level diagram for Hartree orbitals.
 Aufbau Principle and Electron Configurations
Building up the ground-state electronic structure by arranging
the Hartree atomic orbitals in order of increasing energy.

Wolfgang Pauli
(AT,1900-1958) Friedrich Hund
Nobel Prize in Physics(1945) (DE,1896-1997)

(1) Pauli exclusion principle

No two electrons in an atom can have the same set of
four quantum numbers, (n, l, ml, ms).
(2) Hund’s rule
When electrons are added to Hartree orbitals of equal energy,
a single electron enters each orbital before a second one
enters any orbital. If possible, the spins remain parallel.
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Fig. 5.19. The ground-state electron Fig. 5.20. For a many-electron
configurations atom C, orbitals with different l
of the first- and second-period atoms. values have different energies.

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Fig. 5.21. The filling of shells and the structure of the periodic table.
Only the “anomalous” electron configurations are shown.

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 Shells and the Periodic Table
Photoelectron Spectroscopy
➢ Shell
~ a set of orbitals with the same principal quantum number, n
• Average positions of the electron in each of these shells
are close to each other, but far from those of the orbitals
with different value of n. Na: [Ne]3s1 K: [Ar]4s1

➢ Ionization energies of Na (Z=11): 1s2 2s2 2p6 3s1

IE1=0.50 MJ mol-1, IE2=4.56, IE3=6.91, IE4=9.54,
IE5=13.35,
IE6=16.61, IE7=20.11, IE8=25.49, IE9=28.93, IE10=141.37
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➢ Photoelectron spectroscopy (PES)
Determines the energy levels of each orbital by measuring
the ionization energy required to remove each electron from
the atom. Photoelectric effect! (metal atom)
Kinetic energy of ejected electrons is measured by an
energy analyzer.

Fig. 5.22. The energy of

photoelectrons is determined by
measuring the voltage required
to deflect the electrons along a
semicircular pathway between
two charged metallic hemi-
spherical plates in vacuum
so they arrive at the detector.
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➢ Ionization energy
spectrum

Fig. 5.23. Photoelectron spectrum of Ne. Three peaks in the spectrum

indicates that the electrons of neon are organized in three bonding states
of distinct energy values.
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3d, 4d, 4f, and 5f subshells
show exceptional behavior.

Fig. 5.25. The energies of different subshells in the first

97 elements, as determined by PES. 28
 Periodic Properties and Electronic Structure
➢ Trend in the size of radii
● Radii as Z in the same
group (column)
~ due to the exclusion principle
● Radii since Zeff as Z
across a period …
~ due to incomplete shielding
● Change in size:
(Li+–Na+– K+) > (Rb+–Cs+)
~ due to filling d orbitals

Fig. 5.26. Ionic and atomic radii

plotted against atomic number.
➢ Molar volume
~ Affected by (1) atomic size and (2) geometry of bonding

Fig. 5.27. The molar volumes of some elements in their solid states.

Astatine (At) is a short-lived radioactive element.

t1/2 = 8.5 hr for 210At
➢ Ionization
Energy

Fig. 5.28. 1st and 2nd ionization energies of atoms of the first three
periods.
➢ Electron
Affinity

Fig. 5.29. Electron affinities of gaseous atoms of the elements. An asterisk

means that the element does not have a stable anion in the gaseous phase.

Fig. 5-29, p. 227