Foundations and Applications of Quantum Chemistry

Foundations and Applications of
Quantum Chemistry
Dirk Andrae
Theoretical Chemistry
Department of Chemistry, University of Bielefeld
Summer Term 2004
Foundations and Applications of

Quantum Chemistry
or
Frequently Asked Questions
about Chemistry
What are the electrons doing in atoms and molecules?

What is an orbital? How can it be visualized?
What is a chemical bond?
What are the nuclei doing in ordinary matter?
...
What is mind? No matter! What is matter? Never mind.
Outline
1. Historical introduction
2. The Schr
odinger equation for one-particle problems
3. Mathematical tools for quantum chemistry
4. The postulates of quantum mechanics
5. Atoms and the periodic table of chemical elements
6. Diatomic molecules
7. Ten-electron systems from the second row
8. More complicated molecules
1. Historical introduction
(classical mechanics, electrodynamics & chemistry)
2. The Schr
odinger equation for one-particle problems
3. Mathematical tools for quantum chemistry
4. The postulates of quantum mechanics
5. Atoms and the periodic table of chemical elements
6. Diatomic molecules
7. Ten-electron systems from the second row
8. More complicated molecules
FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05
1/ 52-1
Classical mechanics
If I have been able to see further, it was only because I stood on the shoulders of giants.
Isaac Newton in a letter to Robert Hooke
I. Newton (1643-1727)
Philosophi naturalis principia mathematica
(1687, English tr. 1729, German tr. 1872)
F = p =
dp
dt
p = mv
For the first time [. . . ] a single mathematical law could account for phenomena of the
heavens, the tides and the motion of objects on the earth. (Encyclopdia Britannica, 1971)
http://www.lib.cam.ac.uk/Exhibitions/Footprints of the Lion/gravity glory.html
2/ 52-1
Newtons first law of motion (Principle of inertia):

Every body continues in its state of rest, or of uniform motion in
a right line, unless it is compelled to change that state by forces
impressed upon it.
F =o
t
a = v =
(1)
dv
=o
dt
t < t < t
3/ 52-1
Newtons second law of motion (Principle of action):

The change of motion [ i.e. momentum ] is proportional to the
motive force impressed; and is made in the direction of the right line
in which that force is impressed.
Fx
dp
=
F = Fy
=p
dt
Fz
m
v
t
t
px
dr
p = py
= mv = m
dt
pz
(2)
m
F
t
t < t < t
Eq. (2) includes eq. (1) in the special case of constant mass m and
vanishing force (F = o), but applies, in the form F = p , to rockets
(m = m(t)) and even to relativistic dynamics (m meff (v 2)).
4/ 52-1
Newtons third law of motion:

To every action there is always opposed an equal re-action; or the
mutual actions of two bodies upon each other are always equal, and
directed to contrary parts.
t
t < t
Attractive and repulsive forces are combined to the resulting total

forces.
5/ 52-1
Given a set of masses mi with known initial positions r i(t) and velocities v i(t) at a time t.
New positions and velocities at a time t0 = t + t are obtainable
through integration, e.g.
v i(t0) = v i(t) + ai t
ri(t0) = r i(t) + v i(t) t +
ai =
1
ai (t)2
2
1
Fi
mi
(3)
(4)
if the total forces F i are assumed to be constant over t.

Molecular Mechanics & Dynamics
6/ 52-1
Extension to general coordinate systems:

L. Euler (1707-1783)
J. L. dAlembert (1717-1783)
J. L. de Lagrange (1736-1813)
S. D. Poisson (1781-1840)
C. G. J. Jacobi (1804-1851)
W. R. Hamilton (1805-1865)
Action S and Lagrange function L:

S(t1 , t2 ) =
Z t
2
t1
L(qi , qi , t) dt
(5)
2
qi, qi generalized coordinates and

corresponding velocities (i = 1, . . . , f ,
where f is the number of degrees of
freedom)
Principle of stationary action:
S = 0
(6)
7/ 52-1
Definition of generalized conjugate momenta and forces:

pi =
L
,
qi
Fi =
L
qi
(7)
Euler-Lagrange equations (2nd order PDE for each qi (t)):

d L
dt qi
L
= pi Fi = 0
qi
(8)
Transformation from the Lagrange function L to the Hamilton function H:

H(qi, pi , t) =
X
i
(9)
qi pi L(qi , qi, t)
Hamiltons equations (pairs of 1st order PDEs for each qi(t)):

pi =
dpi
H
=
,
dt
qi
qi =
dqi
H
=
dt
pi
(10)
Legendre transformation (A.-M. Legendre, 1752-1833), also known from thermodynamics:
Internal energy U = U (S, V ) Helmholtz free energy A(T, V ) with A = T S U , or

enthalpy H = H(p, S) Gibbs free energy G(p, T ) with G = T S H,
where T = (U/S)V = (H/S)p .
8/ 52-1
In terms of the Poisson bracket, defined for any pair of physical quantities A and B as
!
f
X
A B A B
= {B, A}
{A, B} =
p
q
q
p
i
i
i
i
i=1
the variation of a physical quantity Q in time is simply
(11)
= {H, Q}
Q
(12)
as follows from the generalized chain rule of differentiation.

Thus Hamiltons equations read as
qi = {H, qi } ,
pi = {H, pi}
(13)
In general, if {A, B} = 0, A and B are said to commute.

Consider the generalized coordinates and momenta themselves:
{qj , qk } = 0 ,
{pj , pk } = 0 ,
{pj , qk } = jk
(14)
Coordinates commute with momenta only when different degrees of

freedom are involved.
9/ 52-1
A suitable choice for L has to be made. Consider, e.g., a free particle

with rest mass m moving with velocity v :
non-relativistic case
1
L = T = mv 2 = L(v 2 )
2
relativistic case ( = v/c)

L = mc2
p = mv
p=q
H = p v L = 2T L
1
= mv 2 = T
2
mv
1 2 = L(v 2 )
1 2
mc2
H =pvL= q
=E
2
1
H 2 = m 2 c 4 + c 2 p2 = E 2
=E
Extension to include potential energy V (for conservative potentials):

L=T V
H =T +V =E
(15)
10/ 52-1
Conservation laws and symmetries:

1. If L is translationally invariant in time (homogeneity of time)
H is constant: H = E, conservation of energy E
2. If L is translationally invariant in space (homogeneity of space)
conservation of linear momentum p
3. If L is invariant with respect to orientation in space (rotational
invariance in space, isotropy of space)
conservation of orbital angular momentum l = r p
These are special cases of the Noether theorem which states that
with every continuous symmetry of a dynamical system there is related
a conserved physical quantity (see refs. for a rigorous formulation).
E. Noether (1892-1935)
11/ 52-1
Optics and classical electrodynamics

Chr. Huygens (1629-1695)
Trait
e de la lumi`
ere (1678)
Light is a wave phenomenon (in analogy to water surface waves)
Explanation for reflection, refraction, interference, and polarization
of light.
Huygens principle: Wave phenomena can be understood by superposition of spherical waves.
I. Newton (1643-1727)
Opticks (1704)
Light is composed of particles, which travel along straight lines
geometrical optics.
Observation of the spectral decomposition of white light into light of
all colors.
12/ 52-1
Single slit diffraction a wave phenomenon

(application of Huygens principle)
.
....
....
..
..
...
.........
.
.
... ... ....
.
.
. .
... .... ....
.
.
.. . ...
... ... ..
.. .... ....
.
.
...
.
...
...
.....
...
...
...
...
....
..
...
....
....
..
...
.....
....
...
...
....
....
...
.
.
.
.
.
.
...
.
.
...
...
...
.
.
...
..
..
.
.
.
.
...
.
...
...
...
.
.
..
..
..
...
.
.
.
.
.
...
....
...
.
...
.
..
..
...
.
.
.
.
...
..
...
.
.
...
.
.
.
...
...
...
.
.
...
..
...
...
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
....... ...
..... .....................................
...
.
.........
.......
...............................................................
....................................................................
....
..
... .... .......... ...... .............. ........ .......... .......... ................................................................................................................................................................................................................. ........... .......... ............................ ...... ........... ..... .....
.
...
......... ......... ............... ...... ......... ...... ....... ... ... ... ...
..
... ..... ..... ..... ..... ........... ....... ............. .......... ......................................................
.
.
.
..
.
.
.
.
.
... ....... ............ ..... ......... ... ... ... .. .. ... ..
..
.. .
.
.
.
... ..... ..... ..... ..... ........... ...... .............. ........ .............. ............ ............ .............................................................. ............ ............ .............. .......................... ...... ........... ..... ..... ..... ..... .....
.
.
.. .
... ....
.
.
...
.
. .. .
. . .
..
......
..
.
..
..... ...
... ..... ..... ..... ..... ..... ..... ..... ............ ....... ............... .......... ...................................................................... .... ....................................................................... .......... ............................ ........... ..... ..... ..... ..... .... ..... ....
...
.
.
.
.
.
....... ....... ...........
. . . . . . . .. . . .... ...
.
...
....... ..... .....
....... ....... ..... ........................ ...... ..... ..... ..... ..... ..... ..... .... ..... ....
...
... .... .... .... .... .... .... .... .... ..... ........... ....... ........... ........... ...........
...
.
...
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. . .
. . . . . . .
..
..
..
... ..... ..... ..... ..... ..... ..... ..... ..... ..... ..... ........... ...... ................ .......... .......................................................................................................................................................... .......... ...................... ....... ........... ..... .... ..... .... ..... ..... ..... .... ..... .....
. .. .
.
. ..
.. .. ......... ......... ............. ........ ........ ... ... ... ... ... ... ... ... ... .. ... ... ..
..
... ..... ............... .......... ..... ..... ..... ..... ..... ..... ............ ........ ................ ............. .............
....... ....... ..... ....... ... ... ... ... ... .. .. .. .. .. .. ... .. .. ...
.
.
.
.
.... .... ....... .. . ... . . . .. .. .. .. .. .. . .. .. .
. . . . . . . . . . . . . .. . . ..... .... ....
.
........ .............. ............... .......... ..... ..... ..... .... ..... ..... ............. ......... ......................................................................................... .............................. ..... ..... ..... ..... ..... ..... .... ..... .... ..... .... .... ..... .... .... .....
.
.. .
.
..
. ..
. . . .
.
.
. .
.
. . .
..
.
..
... .... .... .... .... .... .... .... .... .... .... .... .... .... .... .... ..... .... ...... ........................................... ..... ......................................................... ..... ..... ..... .... .... .... ..... .... .... .... ..... .... ..... .... .... .... ..... ....
.
...... ...... ......... .. .. ... ... ... ... ... .. ... .. .. .. ... .. .. .. .. .. ..
.
.. . . . .. . .. .. .. .. .. .. .. .. .. .. ... .. .. ...... .... ....
.... ........ .. ..... ... ... ... .. .. .. .. .. .. ... ... .. .. .. ... ... .. .. .
.. ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ......... ...... .....
...
.. .. .. ... .. .. .. .. .. .. ... .. ... ... ... ... ... ... ... ..... ... ..... ..................................................................... ........ .... ..... ... ... ... ... ... .... ... ... ... ... .. ... ... ... .. ... ... .. ...
... .. .. ... .. .. .. ... .. .. ... ... .. ... .. ... ... ... ... ... ... ... ......... ......... ............... ......... ........... ... ... ... ... ... ... ... ... .. ... ... ... .. ... ... .. ... ... .. .. ... ...
.. ... .. .. ... ... ... .. ... ... ... .. ... ... ... ... ... ... ... ... ... ... ......... ....... ........ .... ......... ............................ ..... .... ..... ..... .... ......... .... ..... .... .... ........ .... .... .... ... ... .... ... ... ...
.. . .. . .. . . . . . . . . . . . . .. . . . . . . . .. .
.
.. ... .. .. .. ... .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .... .. ...
.
... .. .... .... ... ... .. .... ... ... .... .... .... .... .... ... .... ......... .... ... ..... ..... .... ..... ............................................................... .... ..... .... .......... .... .... .... ........ .... ... .... ... .... .. ... .... .. ... ... .... ... ... ....
.. ... .. .. ... ... ... .. ... .. .. .. .. .. ... ... ... .. .. ... ... .. ... ... ... ..... ... ...... .............. ....... .. ..... ... .. ... .. .. ... .. .. .. .. .. .. .. ... .. .. .. .. ... .. .. .. .. .. ..
... .. .. .. .. .. .. ... .. .. .. ... .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ... ........... ................ ..... .... ... .... ... .... ... .... .... .... ... ... .... ... ... ... ... .... ... ... .... .... ... .... ... ....
.. ... ... ... ... ..
.... .... ... .... .... .... ... ... .... .... .... ... ... ... .... ... ... ... .... ... .... ... .... ... .... ..... .... ....
. . ..
. . . . . . ..
......
. . .. .................................................................................................................................................................................................................................................................................................................................................................................................................... ... .. ...
I()
screen .......................................................................................................................
I() = a I0 [ j0(b) ]2
sin (x)
j0(x) =
x
slit
...................................................... .................................................................
(d > )
spherical waves
.................................................................................................................................................................................................................................................................................................................................
...................................................................................................................................................................................................................................................................................................................................
.....
........
.........
...................................................................................................................................................................................................................................................................................................................................
..
..
...
..................................................................................................................................................................................................................................................................................................................................
.................................................................................................................................................................................................................................................................................................................................
plane wave
(k, , I0)
.................................................................................................................................................................................................................................................................................................................................
.................................................................................................................................................................................................................................................................................................................................
.................................................................................................................................................................................................................................................................................................................................
.................................................................................................................................................................................................................................................................................................................................
13/ 52-1
Observation of dark lines in the visible region of the solar spectrum

1802 W. H. Wollaston (1766-1828)
1815 J. Fraunhofer (1787-1826), catalogued over 600 lines
Source: http://www.harmsy.freeuk.com/images/spectrum.jpeg or http://www.coseti.org/solatype.htm
14/ 52-1
Law of electrostatic interaction

1785 Ch. A. Coulomb (1736-1806)
Potential energy V for two charges q1 and q2 at distance r
q q
V =C 1 2
r
In SI units: C = 1/0 with 0 = 40.
(16)
Further experimental study of and theory development for electric and

magnetic phenomena (static and dynamic):
J. B. Biot (1774-1862)
A. M. Amp`
ere (1775-1836)
C. F. Gau (1777-1855)
H. Chr. rsted (1777-1851)
M. Faraday (1791-1867)
F. Savart (1791-1841)
H. Lenz (1804-1865)
W. E. Weber (1804-1891)
15/ 52-1
Maxwells equations of electrodynamics

1861-1864 J. C. Maxwell (1831-1879)
Equations for electric field E (r , t) and magnetic flux density B (r , t)
(in SI units: 0 0c2 = 1)
in the absence of dielectric
or magnetic media
B
t
B
E
1
B 0
0
t
0 E
E+
=o
=0
=j
=
in vacuum (no charges, and

no currents)
=0
j=o
=
B
t
B
1 E
B 2
c t
E
E+
=o
=0
=o
=0
16/ 52-1
In vacuum, every component Xi of E or B has to be a solution of

the dAlembert equation
!
2 Xi
2 Xi
2 Xi
1 2 Xi
+
+
2
=
x2
y 2
z 2
c t2
2
2
1 2
2
+ 2 + 2 2 2 Xi = 0
x2
y
z
c t
(17)
Solutions of eq. (17) are plane waves, representable as real part of
Xi(r , t) = X0 ei(krt)
(18)
They propagate (travel) at the speed of light c in the direction of

the wave vector k (k = |k| = 2/), have amplitude X0 and circular
frequency = 2.
Behaviour of the function Xi(r , t) under differentiation:
Xi (r , t) = i kx Xi(r , t)
x
Xi(r , t) = i Xi (r , t)
t
(19)
so that k2 2 /c2 = kx 2 + ky 2 + kz 2 2/c2 = 0, i.e. c = , with

frequency , wavelength , and wavenumber e = /c = 1/.
17/ 52-1
Plane wave propagating in the z direction
E and B along the z axis
10
8
...............................................................................................
6
4
-0,5
-1
2 -0,5
00
0,5
...
.......
.......
...... ..
.
.....
....
..
..
....
....
....
....
..
..
....
....
....
....
..
..
....
....
....
....
..
..
....
....
....
....
..
..
....
....
....
....
..
...........................................................................................................................................................................................................................................................................................................................................................................
..
..
..
..
..
..
..
..
..
..
..
..
..
..
...
z
...............................................................................................
12
-1
Isovalue lines in the xz plane
...............................................................................................
0
0,5
k kEB
...............................................................................................
Experimental generation of electromagnetic waves (oscillating dipole

radiation in the radiofrequency range), and identification of light as
electromagnetic radiation
1887 H. R. Hertz (1857-1894)
18/ 52-1
Chemistry
Law of conservation of mass:
1748 / 1760 M. W. Lomonossov (1711-1765)
1785 A. L. Lavoisier (1743-1794)
There is no measurable change in mass during a chemical reaction:
the mass of the products is equal to the mass of the reacting substances.
3 g hydrogen + 24 g oxygen 27 g water
Law of constant proportions:
1799 J. L. Proust (1754-1826)
Different samples of a substance contain its elementary constituents
(elements) in the same proportions.
water:
m(hydrogen) : m(oxygen) = 1 : 7.937
19/ 52-1
The chemical elements

(known before 1800, though not necessarily in elemental form)
element symbols introduced in 1811 by J. J. Berzelius (1779-1848)
H
Be
Mg
Al
Ca
Sr
Ba
Ti
Cr Mn Fe Co Ni Cu Zn
Zr
Mo
Ag
Pt Au Hg
Cl
As
Sn Sb Te
Pb Bi
U
20/ 52-1
J. Dalton (1766-1844)
A new system of chemical philosophy
(Part I 1808, Part II 1810, Part III 1827)
Atom hypothesis (1805):

All substances consist of small particles
of matter, called atomsa, of several different kinds, corresponding to the different
elements.
a from Greek

: undivisible, indivisible
Source: http://www.nmsi.ac.uk/piclib/images/preview/10322897.jpg
21/ 52-1
Law of simple multiple proportions:

When two elements combine to form more than one compound, the
weights of one element that combine with the same weight of the
other are in the ratios of small integers.
(derived by J. Dalton from theory, i.e. from his atom hypothesis)
compound Ak Bl
CO
CO2
N2 O
NO
N 2 O3
(NO2, N2 O4)
N 2 O5
m(A)
1 1.000
1 1.000
1 1.000
1 1.000
1 1.000
1 1.000
1 1.000
:
:
:
:
:
:
:
m(B)
1 1.332
2 1.332
1 0.571
2 0.571
3 0.571
4 0.571
5 0.571
22/ 52-1
The table of the chemical elements

(18001849)
H
Li
Be
Na Mg
Al
Si
Cl
Ca
Sr
Ti
Y
Zr Nb Mo
Ba
Ta W
La Ce
Th
Nd
Ru Rh Pd Ag Cd
Os
Ir
Pt Au Hg
Tb
As Se Br
Sn Sb Te
Pb Bi
Er
23/ 52-1
Avogadros law:
1811 A. Avogadro (1776-1856)
1858 S. Cannizzaro (1826-1910)
Equal numbers of molecules are contained in equal volumes of all
dilute gases under the same conditions.
the correct chemical formula for water is H2O, not HO
Spectral analysis
1859 R. W. Bunsen (1811-1899) & G. R. Kirchhoff (1824-1887)
discovery of rubidium, Rb, and caesium, Cs
Periodic table of chemical elements
1869 D. I. Mendeleev (1834-1907) / J. L. Meyer (1830-1895)
prediction of new chemical elements
24/ 52-1
hydrogen
(2 vols.)
hydrogen
(1 vol.)
carbon monoxide
(2 vols.)
oxygen
(1 vol.)
water vapour
(2 vols.)
chlorine
(1 vol.)
hydrogen chloride
(2 vols.)
oxygen
(1 vol.)
carbon dioxide
(2 vols.)
KH
25/ 52-1
Solar spectrum, visible region (http://mesola.obspm.fr/form spectre.html)
Emission spectrum of sodium, Na (http://scidiv.bcc.ctc.edu/wv/spect/sodium em spectrum2.html)
(F)
H
(C)
H
Emission spectrum of hydrogen, H (http://astro.u-strasbg.fr/~koppen/discharge/)
26/ 52-1
Source: http://www.physics.brown.edu/Studies/Demo/modern/demo/em.gif
27/ 52-1
Rb and Cs discovered by spectral analysis

(Bunsen & Kirchhoff, 1859-1863)
H
Li
Be
Na Mg
Al
Si
Cl
Ca
Rb Sr
Ti
Y
Zr Nb Mo
Cs Ba
Ta W
La Ce
Th
Nd
Ru Rh Pd Ag Cd
Os
Ir
Pt Au Hg
Tb
As Se Br
Sn Sb Te
Pb Bi
Er
28/ 52-1
Prediction of existence and properties of Sc, Ga, and Ge

(Mendeleev, 1869/1870)
H
3
Li
Be
11
12
Na Mg
19
K
37
20
55
31
32
33
34
35
24
Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
41
42
40
56
73
Cs Ba
44
57
58
46
47
48
50
Ru Rh Pd Ag Cd
74
Ta W
La Ce
45
30
Cl
23
Zr Nb Mo
29
17
22
28
16
Ti
39
27
15
21
38
26
14
Si
Ca Sc
Rb Sr
25
13
Al
79
80
76
77
78
Os
Ir
Pt Au Hg
82
60
65
68
Tb
Er
90
92
52
53
83
Pb Bi
Nd
Th
51
Sn Sb Te
29/ 52-1
The periodic table of the chemical elements

(1850-1899)
IA
1
VIIIA
2
10
Li
Be
Ne
Na Mg IIIB IVB VB VIB VIIB
11
12
19
K
37
IIA
IIIA IVA VA VIA VIIA He
14
15
16
17
18
Si
Cl
Ar
29
32
33
34
35
36
21
22
23
24
Ti
Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
41
42
38
39
40
Rb Sr
Zr Nb Mo
Cs Ba
Ta W
Ra
55
IB IIB Al
Ca Sc
20
56
73
74
25
13
VIII
26
44
27
45
28
46
47
30
48
Ru Rh Pd Ag Cd
79
80
31
49
50
In
Sn Sb Te
51
81
82
83
52
76
77
78
Os
Ir
Pt Au Hg Tl Pb Bi Po
62
63
64
53
54
Xe
84
88
57
58
59
60
La Ce Pr Nd
89
90
Ac Th
65
66
67
68
69
70
Sm Eu Gd Tb Dy Ho Er Tm Yb
92
30/ 52-1
Development since about 1900

1884/1885 J. Balmer (1825-1898): Empirical formula for visible hydrogen spectral line wavelengths (RH Rydberg constant for hydrogen)

1
1
1
n2
e = = RH
2
=C 2
(C = 4/RH , n > 2)
n 4
4 n
1895 W. C. R
ontgen (1845-1923): Discovery of X rays
1896 A. H. Becquerel (1852-1908): Discovery of natural radioactivity
1897 J. J. Thomson (1856-1940): Cathode rays are beams of free
electrons
1900 M. Planck (1858-1947): Spectral distribution of the radiation
energy density inside a black body (cavity at temperature T with
a small hole, h Planck constant)
8 2 h
u (T ) =
,
c3 ex 1
x=
h
,
kB T
[u ] = J s m3
31/ 52-1
Oscillators in the wall of the cavity emit or absorb radiation energy

only in quantized form (quantum hypothesis)
h
1 1034 J s
2
Previously known approximate laws are included as limiting cases:
E = n ,
= h = ~ ,
~=
8 2
h kBT :
u (T ) =
(Rayleigh-Jeans)
kB T
c3
!
8 h 3
h
h kBT :
u (T ) =
(Wien)
exp
c3
kB T
The total energy density of the radiation field inside the cavity is
proportional to T 4
Z
8 5 kB4
u (T ) d = C T ,
C=
,
[u] = J m3
u(T ) =
3
15
(hc)
0
(this is not the Stefan-Boltzmann law)
1905 A. Einstein (1879-1955): Explanation of the photoeffect (photons); theory of special relativity, conservation of mass-energy
4
E = mc / 1 =
m 2 c 4 + c 2 p2 ,
= v/c
32/ 52-1
1910/1913 F. Soddy (1877-1956) & F. W. Aston (1877-1945): Discovery and mass spectrometric detection of isotopes (e.g. 1H, 2H
for hydrogen; 12 C, 13C for carbon; 35Cl, 37 Cl for chlorine)
1911 E. Rutherford (1871-1937): The atom has a very small nucleus,
which carries almost the total atomic mass and has positive charge
qN = Ze (Z nuclear charge number). This nucleus is surrounded
by electrons (each has charge qe = e).
Size of the atomic nucleus: 1015 m
1912 M. von Laue (1879-1960): Single-crystal diffraction with X rays
Size of the atoms: 1010 m = 1
A
1913 H. Moseley (1887-1915): Direct determination of the nuclear
charge number Z from the frequency of emitted X rays:
Z2
1913/1916 N. Bohr (1885-1962), A. Sommerfeld (1868-1951):
The one-electron atom as a miniaturized planetary system: In stationary states, the electron moves on elliptical orbits (the nucleus
33/ 52-1
being located in one focus) and has energies

e2
Eh =
,
0 a 0
1 Z2
En =
E ,
2 n2 h
0 ~2
a0 =
m e e2
Electromagnetic radiation is emitted or absorbed according to

energy differences between stationary states

1
1
En E m
= R Z 2
,
e =
hc
m 2 n2
m e e4
R =
80 2h3 c
(R Rydberg constant for nucleus with infinite mass)

The Balmer formula is included for Z = 1 and n > m = 2.
This model failed to describe the simplest two-electron systems
(He, H2 ), and thus to understand the chemical bond
1920 The name proton is given to the nucleus of 1H (E. Rutherford)
1921 O. Stern (1888-1969) & W. Gerlach (1889-1979): A beam of Ag
atoms is split up into two parts by an inhomogeneous magnetic
field. Detection of atomic spin and associated magnetic dipole
moment (to spin - to rotate quickly around the figure axis)
34/ 52-1
1923 A. H. Compton (1892-1962): Elastic scattering of X rays (waves

behave like particles)
out = in + ,
= C (1 cos ()) ,
C =
h
me c
( scattering angle, C Compton wavelength)

1924 S. N. Bose (1894-1974) & A. Einstein: Bose-Einstein statistics
for photons and other particles with integer spin (spin quantum
number s = n/2, n = 2k), i.e. for bosons

1925 L. de Broglie [fr.
] (1892-1987): For the photon (m = 0)
q
h
h
2 ~
= =
= ~k
c
Linear momentum p (particle property) associated with wavelength (wave property), suggestion to transfer this relation to
particles
1925 S. A. Goudsmit (1902-1978) & G. E. Uhlenbeck (1900-1988):
Postulate of electron spin (intrinsic non-classical angular momentum)
E=
m2 c4 + c2p2 = cp = h = ~
p=
35/ 52-1
1925 W. Pauli (1900-1958): No two electrons may simultaneously

occupy the same quantum state (Pauli exclusion principle)
1925/1926 W. Heisenberg (1901-1976) & M. Born (1882-1970): Matrix mechanics (first version of quantum mechanics)
1926 E. Schr
odinger (1887-1961): Wave mechanics (second version
of quantum mechanics)
Proof of equivalence of matrix mechanics and wave mechanics;
Schr
odinger equation for stationary states of the one-electron
atom with atomic nucleus of charge number Z fixed at the origin:
~2 2
+V =
2me
~2 2
+V
2me
= E,
V =
Z e2
0 r
Electron spin is not included, has to be added phenomenologically

1926 E. Fermi (1901-1954) & P. A. M. Dirac (1902-1984): FermiDirac statistics for electrons and other particles with half-integer
spin (spin quantum number s = n/2, n = 2k+1), i.e. for fermions
1927 W. Heisenberg: Uncertainty principle, in modern form:
x px ~/2
36/ 52-1
The picture of a trajectory, where position and velocity (linear

momentum) are exactly known at every instant of time, is wrong!
1927 W. H. Heitler (1904-1981) & F. London (1900-1954): Successful
application of the Schr
odinger equation to the H2 molecule, the
covalent chemical bond is understood for the first time
1927 C. J. Davisson (1881-1958) & L. H. Germer (1896-1971): Singlecrystal diffraction with electron beams (particles behave like
waves)
1928 P. A. M. Dirac: Dirac equation for stationary states of the oneelectron atom with atomic nucleus of charge number Z fixed at
the origin:
2
b
b
b
V + me c
0
c pz
c ( px i py )
0
V + me c
c (pbx + i pby )
c pbz
= E
2
b
b
b
c
p
c
(
p
i
p
)
V
m
c
0
z
x
y
e
2
c (pbx + i pby )
c pbz
0
V me c
1
pbx

Z e2
b = pby = i~ ,
V =
,
=
p
2
3
0 r
pbz
4
37/ 52-1
Electron spin is naturally included, prediction of anti-particles

(positron)
1932 J. Chadwick (1891-1974): Discovery of the neutron
1932 C. D. Anderson (1905-1991): Discovery of the positron
38/ 52-1
Summary
Matter has a discrete structure, not a continuous structure! It can be
thought of being composed of atoms (built from atomic nuclei and
electrons), which somehow form molecules, crystals, and all other
material things of this world.
The atomic mass is almost completely located in the atomic nucleus.
This nucleus (with mass number A = Z + N ) is composed of
- protons (with charge qp = e, their number Z determines the chemical element), and
- neutrons (with charge qn = 0, their number N determines the
isotope).
The nucleus is surrounded by
- electrons (with charge qe = e), which have kinetic energy and
are held to the nucleus by electrostatic attraction.
39/ 52-1
Electrons, protons, and neutrons are fermions with spin quantum

number s = 1/2.
Quantum mechanics provides the theory to understand why electrons bind to atomic nuclei (without collapsing into the nucleus) to
form stable atoms, and how the atoms thus formed combine to form
molecules and undergo chemical reactions.
Let us consider chemistry as the science which studies the structure, the properties and the behaviour of electrons distributed around
atomic nuclei (this includes e.g. molecular structure, molecular properties, and any kind of chemical reactions). One can realize that we
have achieved for chemistry a situation comparable to the situation
of classical mechanics after the discovery of Newtons laws (compare
the quote on page 2 / 52-1).
40/ 52-1
The underlying physical laws necessary for the mathematical theory

of a large part of physics and the whole of chemistry are thus completely known, and the difficulty is only that the exact application of
these laws leads to equations much too complicated to be soluble.
It therefore becomes desirable that approximate practical methods of
applying quantum mechanics should be developed, which can lead
to an explanation of the main features of complex atomic systems
without too much computation.
P. A. M. Dirac, Proc. R. Soc. London, A 123 (1929) 714-733
41/ 52-1
Die Quantenchemie mat sich nicht weniger an, als s

amtliche chemischen und physikalischen Materialeigenschaften rein theoretisch vorausberechnen zu k
onnen, nur auf Grund eines einzigen mathematischen Gesetzes, n
amlich der Schr
odingerschen Differentialgleichung
und der in ihr formulierten Grundeigenschaften der Materie.
Kvantova himi stavit svoe zadaqe rassqityvat~ qisto teoretiqeski himiqeskie i fiziqeskie svostva vewestva, ishod iz odnogo
matematiqeskogo zakona differencial~nogo uravneni Xredingera i teh osnovnyh svostv materii, kotorye v nem sformulirovany.
H. Hellmann (1903-1938), Front Nauki i Tehniki (1936) 6:34-48, 7:39-50
(orig. ms. in German ms., 47 p.)
Quantum chemistry claims nothing less than the capability of the

theoretical prediction of all chemical and physical material properties, simply on the basis of one single mathematical law, i.e. the
Schr
odinger differential equation and the basic properties of matter
formulated therein.
42/ 52-1
The first textbooks on quantum chemistry
1935
1937 (Russ. & Ger. eds.)

1944
43/ 52-1
[. . .] Quantum mechanics is essentially mathematical in character, and an understanding of the subject without thorough knowledge of the mathematical methods
involved and the results of their application cannot be obtained. The student not
thoroughly trained in the theory of partial differential equations and orthogonal
functions must learn something of these subjects as he studies quantum mechanics. [. . .]
Linus Pauling, E. Bright Wilson, Jr.: Introduction to Quantum Mechanics With
Applications to Chemistry , McGraw-Hill, New York, 1935, Preface
In so far as quantum mechanics is correct, chemical questions are problems in applied mathematics. In spite of this, chemistry, because of its complexity, will not
cease to be in large measure an experimental science, even as for the last three
hundred years the laws governing the motions of celestial bodies have been understood without eliminating the need for direct observation. No chemist, however,
can afford to be uninformed of a theory which systematizes all of chemistry even
though mathematical complexity often puts exact numerical results beyond his immediate reach. [. . .]
H. Eyring, J. Walter, G. E. Kimball: Quantum Chemistry , Wiley, New York, 1944,
Preface
44/ 52-1
Sowohl die Materie als auch die elektromagnetische Strahlung kann man sich in
keiner Weise befriedigend anschaulich vorstellen (welches Modell man auch verwendet), wenngleich einige Aspekte der beiden physikalischen Entit
aten bestimmte
Analogien mit einem korpuskularen Modell aufweisen und andere mit einem Wellenmodell. [...] Wenn man das korpuskulare Modell allzu w
ortlich nimmt, d. h. wenn
man Photonen, Elektronen usw. als gew
ohnliche K
orper von sehr kleinen Dimensionen betrachtet, macht man den gleichen Fehler, wie wenn man aus den bekannten
Analogien zwischen elektrischen Str
omen und Fl
ussigkeitsstr
omungen den Schlu
z
oge, da Elektrizit
at eine gew
ohnliche Fl
ussigkeit ist.
J. D. Fast: Entropie. Philips, Eindhoven, 1960, 4.2, p. 175
No completely satisfactory pictorial representation can be made of either matter or
electromagnetic radiation, although some aspects of both physical realities show
analogy with a corpuscular model and others with a wave model. [...] To take
the corpuscular model too literally, i.e. to regard photons, electrons etc. as normal
bodies on a greatly reduced scale, is to make the same mistake that would be
made by concluding from the well-known analogy between electrical currents and
hydraulic currents that electricity is a normal fluid.
J. D. Fast: Entropy.
171-172
2nd ed., Gordon & Breach, New York, 1968, 4.2, pp.
45/ 52-1
Naturwissenschaft l
asst sich mit Bildern popularisieren, aber nur mit
Mathematik verstehen
H. Tetens: Die Grenze, DIE ZEIT 37/1999 (http://www.zeit.de/archiv/1999/37/public files)
Science can be popularized with pictures, but can be understood only

with mathematics
... this is also a good point to start thinking about what understanding in science means. With
Newtons laws we know how a mass behaves, but we still do not know what mass is. It seems to
be unimportant to know that. And with the Schr
odinger equation we have a tool in our hands to
find out how electrons behave in ordinary matter, but we do not know what an electron is.
46/ 52-1
Plus les sciences physiques ont fait de progr`

es, plus elles ont tendu `
a rentrer dans le
domaine des math
ematiques, qui est une esp`
ece de centre vers lequel elles viennent
converger. On pourrait m
eme juger du degr
e de perfection auquel une science est
parvenue, par la facilit
e plus ou moins grande, avec laquelle elle se laisse aborder
par le calcul.
douard Mailly: Essai sur la vie et les
L. A. J. Quetelet (1796-1874), 1827 citation dapr`
es: E
ouvrages de L.-A.-J. Quetelet, F. Hayez, Bruxelles, 1875, p. 55
The more progress physical sciences make, the more they tend to enter the domain
of mathematics, which is a kind of centre to which they all converge. We may even
judge the degree of perfection to which a science has arrived by the facility with
which it may be submitted to calculation.
A. Quetelet (1796-1874) ref. for engl. version: GAUSSIAN fortune quotation
47/ 52-1

(1900-1949)
IA
1
VIIIA
2
10
Li
Be
Ne
Na Mg IIIB IVB VB VIB VIIB
11
12
19
K
37
IIA
IIIA IVA VA VIA VIIA He
IB IIB Al
14
15
16
17
18
Si
Cl
Ar
29
32
33
34
35
36
21
22
23
24
Ca Sc
Ti
41
42
20
25
13
VIII
47
40
Zr Nb Mo Tc Ru Rh Pd Ag Cd
77
78
Cs Ba
Hf Ta W Re Os
Ir
Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra
58
63
64
87
88
74
75
76
79
48
31
39
73
46
30
38
72
45
28
Rb Sr
56
44
27
55
43
26
80
49
50
In
Sn Sb Te
51
81
82
83
52
84
53
54
Xe
85
86
57
59
60
61
62
65
66
67
68
69
70
71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89
90
91
Ac Th Pa
92
93
94
95
96
Np Pu Am Cm
48/ 52-1

(1950-1999)
1
10 11 12 13 14 15 16 17 18
He
10
Li
Be
Ne
11
12
Na Mg
19
K
37
Ar
31
32
33
34
35
36
24
41
42
47
30
18
Cl
23
38
39
40
Rb Sr
Zr Nb Mo Tc Ru Rh Pd Ag Cd
77
78
Cs Ba
Hf Ta W Re Os
Ir
Pt Au Hg Tl Pb Bi Po At Rn
106
109
Fr Ra
55
87
56
88
72
73
74
75
76
46
29
17
22
45
28
16
Ti
44
27
15
21
43
26
14
Si
Ca Sc
20
25
13
Al
79
48
80
104
111
112
Rf Db Sg Bh Hs Mt Ds
X (X)
57
58
65
66
105
59
60
107
61
108
62
63
110
64
49
50
In
Sn Sb Te
81
82
67
51
83
52
84
53
54
Xe
85
86
114
116
118
(X)
(X)
(?)
68
69
70
71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89
90
91
Ac Th Pa
92
93
94
95
96
97
98
Np Pu Am Cm Bk Cf
99
100
101
102
103
Es Fm Md No Lr
49/ 52-1
Symbols and names of the chemical elements (Nov. 2003, http://www.iupac.org/)

Ac
Ag
Al
Am
Ar
As
At
Au
B
Ba
Be
Bh
Bi
Bk
Br
C
Ca
Cd
Ce
Cf
Cl
Cm
Co
Cr
Cs
Cu
Db
Actinium
Silver
Aluminium
(Aluminum)
Americium
Argon
Arsenic
Astatine
Gold
Boron
Barium
Beryllium
Bohrium
Bismuth
Berkelium
Bromine
Carbon
Calcium
Cadmium
Cerium
Californium
Chlorine
Curium
Cobalt
Chromium
Caesium
(Cesium)
Copper
Dubnium
Ds
Dy
Er
Es
Eu
F
Fe
Fm
Fr
Ga
Gd
Ge
H
He
Hf
Hg
Ho
Hs
I
In
Ir
K
Kr
La
Li
Lr
Lu
Md
Mg
Darmstadtium
Dysprosium
Erbium
Einsteinium
Europium
Fluorine
Iron
Fermium
Francium
Gallium
Gadolinium
Germanium
Hydrogen
Helium
Hafnium
Mercury
Holmium
Hassium
Iodine
Indium
Iridium
Potassium
Krypton
Lanthanum
Lithium
Lawrencium
Lutetium
Mendelevium
Magnesium
Mn
Mo
Mt
N
Na
Nb
Nd
Ne
Ni
No
Np
O
Os
P
Pa
Pb
Pd
Pm
Po
Pr
Pt
Pu
Ra
Rb
Re
Rf
Rh
Rn
Ru
Manganese
Molybdenum
Meitnerium
Nitrogen
Sodium
Niobium
Neodymium
Neon
Nickel
Nobelium
Neptunium
Oxygen
Osmium
Phosphorus
Protactinium
Lead
Palladium
Promethium
Polonium
Praseodymium
Platinum
Plutonium
Radium
Rubidium
Rhenium
Rutherfordium
Rhodium
Radon
Ruthenium
S
Sb
Sc
Se
Sg
Si
Sm
Sn
Sr
Ta
Tb
Tc
Te
Th
Ti
Tl
Tm
U
V
W
Xe
Y
Yb
Zn
Zr
Sulphur
(Sulfur)
Antimony
Scandium
Selenium
Seaborgium
Silicon
Samarium
Tin
Strontium
Tantalum
Terbium
Technetium
Tellurium
Thorium
Titanium
Thallium
Thulium
Uranium
Vanadium
Tungsten
(Wolfram)
Xenon
Yttrium
Ytterbium
Zinc
Zirconium
50/ 52-1
Prefixes for physical units

n
1
2
3
6
9
12
15
18
21
24
Powers of ten (10n), prefixes, and symbols

101
102
103
106
109
1012
1015
1018
1021
1024
decicentimillimicronanopicofemtoattozeptoyocto-
d
c
m
n
p
f
a
z
y
10+1
10+2
10+3
10+6
10+9
10+12
10+15
10+18
10+21
10+24
decahectokilomegagigaterapetaexazettayotta-
da
h
k
M
G
T
P
E
Z
Y
51/ 52-1
Fundamental physical constantsa

Quantity
speed of light in vacuum
magnetic constant
(vacuum permeability)
electric constant 1/(0 c2 )
(vacuum permittivity)
Planck constant
h/(2)
elementary charge
electron mass
proton mass
neutron mass
proton-electron mass ratio
Sommerfeld fine-structure constant
40 ~c/e2
Compton wavelength h/(me c)
Bohr magneton e~/(2me)
nuclear magneton e~/(2mp)
Rydberg constant 2 me c/(2h)
Avogadro constant
1
m(12 C)
atomic mass constant 12
Faraday constant NAe
molar gas constant
Boltzmann constant R/NA
Value in SI unitsb
Symbol
c, c0
0
299792458
4
8.854187817 . . .
1012
h
~
e
me
mp
mn
mp /me
1
C
B
N
R
NA , L
mu
F
R
kB
6.6260693(11)
1.05457168(18)
1.60217653(14)
9.1093826(16)
1.67262171(29)
1.67492728(29)
1836.15267261(85)
7.297352568(24)
137.03599911(46)
2.426310238(16)
927.400949(80)
5.05078343(43)
10973731.568525(73)
6.0221415(19)
1.66053886(28)
96485.3383(83)
8.314472(15)
1.3806505(24)
107
1034
1034
1019
1031
1027
1027
m s1
N A2
F m1
Js
Js
C
kg
kg
kg
103
1012
1026
1027
1023
1027
1023
m
J T1
J T1
m1
mol1
kg
C mol1
J mol1 K1
J K1
a CODATA recommended values 2002 (http://physics.nist.gov/constants/).

b The standard deviation uncertainty in the least significant digits is given in parentheses.
52/ 52-1

Foundations and Applications of Quantum Chemistry

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Foundations and Applications of Quantum Chemistry

Загружено:

Авторское право:

Доступные форматы

Foundations and Applications of

Summer Term 2004

Foundations and Applications of

What are the electrons doing in atoms and molecules?

What is mind? No matter! What is matter? Never mind.

http://www.lib.cam.ac.uk/Exhibitions/Footprints of the Lion/gravity glory.html

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05

Newtons first law of motion (Principle of inertia):

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05

Newtons second law of motion (Principle of action):

Newtons third law of motion:

Attractive and repulsive forces are combined to the resulting total

if the total forces F i are assumed to be constant over t.

Extension to general coordinate systems:

Action S and Lagrange function L:

qi, qi generalized coordinates and

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05

Definition of generalized conjugate momenta and forces:

Euler-Lagrange equations (2nd order PDE for each qi (t)):

Transformation from the Lagrange function L to the Hamilton function H:

Hamiltons equations (pairs of 1st order PDEs for each qi(t)):

Legendre transformation (A.-M. Legendre, 1752-1833), also known from thermodynamics:

Internal energy U = U (S, V ) Helmholtz free energy A(T, V ) with A = T S U , or

as follows from the generalized chain rule of differentiation.

In general, if {A, B} = 0, A and B are said to commute.

Coordinates commute with momenta only when different degrees of

A suitable choice for L has to be made. Consider, e.g., a free particle

relativistic case ( = v/c)

Extension to include potential energy V (for conservative potentials):

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05

Conservation laws and symmetries:

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05

Optics and classical electrodynamics

Single slit diffraction a wave phenomenon

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05

Observation of dark lines in the visible region of the solar spectrum

Source: http://www.harmsy.freeuk.com/images/spectrum.jpeg or http://www.coseti.org/solatype.htm

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05

Law of electrostatic interaction

Further experimental study of and theory development for electric and

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05

Maxwells equations of electrodynamics

in vacuum (no charges, and

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-05

In vacuum, every component Xi of E or B has to be a solution of

They propagate (travel) at the speed of light c in the direction of

so that k2 2 /c2 = kx 2 + ky 2 + kz 2 2/c2 = 0, i.e. c = , with

Plane wave propagating in the z direction

E and B along the z axis

Isovalue lines in the xz plane

Experimental generation of electromagnetic waves (oscillating dipole

m(hydrogen) : m(oxygen) = 1 : 7.937

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-12

The chemical elements

Atom hypothesis (1805):

Law of simple multiple proportions:

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-12

The table of the chemical elements

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-12

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-12

FAQC D. Andrae, Theoretical Chemistry, U Bielefeld 2004-05-12

Solar spectrum, visible region (http://mesola.obspm.fr/form spectre.html)

Emission spectrum of sodium, Na (http://scidiv.bcc.ctc.edu/wv/spect/sodium em spectrum2.html)

Emission spectrum of hydrogen, H (http://astro.u-strasbg.fr/~koppen/discharge/)