Atomic units; Molecular Hamiltonian;

Born-Oppenheimer approximation
1. Atomic Units
The atomic units have been chosen such that the fundamental electron properties are all
equal to one atomic unit. (me=1, e=1, = h/2 = 1, ao=1, and the potential energy in
the hydrogen atom (e2/40ao = 1).
Symbol

Quantity

Value in a.u.

Value in SI units

me

Mass (Electron mass)

9.109410-31Kg

Charge (Electron charge)

1.602210-19C

a0

Length (Bohr first radius

0.5291810-10m

( /(kme2))
2

EH

Energy (EH= 2/mea02)

27.2114eV=4.359710-18J

Angular momentum

1.054610-34Js

vB

Velocity (c=e2/40 )

2.187691106ms-1

Time (0= /EH)

2.41888410-17s

40

Vacuum permittivity

1.11310-10C2/(Jm)

d0

Electric dipole moment (ea0)

8.47810-30Cm

e2a02EH-1

Electric polarizability

1.64910-41 C2m2J-1

Derived units
2

6.62610-34Js

137.036

2.998108m/s

9.27410-24J/T

Nuclear magneton

2.72310-4

5.05110-27J/T

Vacuum permeability (4/c2)

6.62910-4

410-7 Js2/(mC2)

E0

Electric field strength

5.14231011V/m

Plancks constant

Speed of light (c=vB/)

Bohr magneton (e /2me)

In atomic units the mass of a proton (1.6726 x 10-27 kg) would be 1836.15 au, and the
reduced mass of the hydrogen molecule (.503913 g/mol) would be 925.260 au.
The use of atomic units also simplifies Schrdinger's equation. For example the
Hamiltonian for an electron in the Hydrogen atom would be:
SI units:

2
1 e2
2
2me
40 r

Atomic units:

1 2 1

2
r

Other frequently used energy units:

1a.u. = 27.212eV = 627.51Kcal/mol = 219470 cm-1

1Kcal/mol = 4.184KJ/mol

Debye: 1ea0 = 2.54181De; 1De=0.3934ea0

Energy conversion factors

Hartree(a.u.)
KJ/mol
Kcal/mol
eV
cm-1

Hartree(a.u.)
1
0.00038088
0.0015936
0.036749

KJ/mol
2625.5
1
4.184
96.485

Kcal/mol
627.51
0.23901
1
23.061

eV
27.212
0.010364
0.043363
1

cm-1
219470
83.593
349.75
8065.5

4.5563E-06

0.011963

0.0028591

0.00012398

Other fundamental constants:

Boltzmanns constant:

k=1.3806610-23J/K

Avogadros number:

NA=6.022051023mol-1

Rydberg constant:

R=1.097373107m-1

Compton wavelength of electron:

C=2.42630910-12m

Stefan-Boltzmann constant: =5.67032108W/(m2K4)

Electric field unit:
Field=X+a means that an electric field of a*10-4 a.u. is applied along the X direction.
1.a.u.=Hartree/(charge*bohr) = 27.2114*1.6 10-19J/(1.6 10-19C * 5.29177 10-11 m)
1 a.u. = 5.1423 1011 V/m
1 a.u. = 51.423 V/
Ef(V/)=51.423Ef(a.u.)
Field=X+1000 means a field of 0.1a.u. (5.1423V/) is applied along the X direction
For UV-Vis spectra:
E(eV)=const./(nm) 1240/(nm). (nm) 1240/E(eV)
2. Basic concepts
- molecular Hamiltonian
- form of many-electron wave-functions
(Slater determinants (SD) and linear combinations of SD)
- Hartree-Fock (HF) approximation
- more sophisticated approaches which use the HF method as a starting point
(correlated post-Hartree Fock methods)

Approximations made in the framework of the Hartree-Fock-Roothaan-Hall

theory
2

Molecular Hamiltonian
The non-relativistic time-independent Schrdinger equation:
H|>=E|>
H Hamiltonian operator for a system of nuclei and electrons

riA | riA || ri R A |

rij | rij || ri r j |

RAB | RAB || RA RB |
i, j electrons (N)
A, B nuclei (M)

A molecular coordinate system

N

N 1 N

M 1 M

ZA
Z A ZB
1 2
1
1
H
i
2A

2
2M
riA
r
R
i 1
A
1 A
i 1
A
1
i 1 j i ij
1 B

A AB

Te

TN

2
2
2
i2 2

x
y i2
z i2
i

VeN

Vee

(1)

VNN

the major challenge in solving the time-independent Schrodinger

equation

MA - the ratio of the mass of nucleus A to the mass of an electron

ZA the atomic number of nucleus A
Te the operator for the kinetic energy of the electrons
TN the operator for the kinetic energy of the nuclei
VeN the operator for the Coulomb attraction between electrons and nuclei
Vee the operator for the repulsion between electrons
VNN the operator for the repulsion between nuclei
(1) represents the general problem
to be separated in two parts: electronic and nuclear problems
Exact solution for systems containing more than one electron is unknown!
approximations, approximations,

Born-Oppenheimer Approximation
=(x1,,xN, X1,,XM)
The term VeN in the Hamiltonian prevents any wave-function (x,X) solution of the time
independent Schrdinger equation from being written as a product of an electronic
wavefunction and a nuclear wavefunction.
Thus, we need approximations so that we can factorize the wavefunction!
The nuclei are much heavier than electrons (mproton=1836me)
they move much more slowly
the nuclei can be considered frozen in a single arrangement
(molecular conformation)
the electrons can respond almost instantaneously to any change
in the nuclear position
On the time scale where the electrons move around, the nuclei are essentially fixed.

The electrons in a molecule are moving in the field of fixed nuclei. Neglecting the spin of
nuclei, the total wavefunction is written as:
=e(x,{R})

N(R)

factorized (separable) form

On this basis:
2-nd term in (1) can be neglected
5-th term in (1) is a constant
e is parametrically dependent on the positions of the nuclei
SE is separated in 2 SEs, one for electrons and one for nuclei
two Hamiltonians

Electronic Hamiltonian:
-

describes the motion of N electrons in the field of M fixed point charges

He (R)

i 1

1 2
i
2

Z A N 1

r
A 1 iA
i 1

i 1

r
j i

(2)

ij

He(R) means that He depends on the nuclei positions (R coordinate does not appear
in He but riA)
Electronic Schrdinger equation:
He(R)e(x;R)=Ee(R)e(x;R)

(3)

e=e(x;R)

(4)

Ee = Ee(R)

(5)

(4) - is the electronic wave-function which describes the motion of the electrons
- describes electronic states for fixed nuclear coordinates {R}
- explicitly depends on the electronic coordinates

- parametrically depends on the nuclear coordinates because H is a function of

the positions R of the nuclei
Another approximation: for each value of the nuclear positions, the electronic system is
in the electronic ground state, corresponding to the lowest Ee(R).
parametric dependence
-

the nuclear coordinates do not appear explicitly in e.

from the point of view of the electrons, the nuclear degrees of freedom are fixed

a different electronic wave-function is obtained for each nuclear configuration

The total energy:

Epot
tot (R ) E e

M 1 M

Z A ZB
R AB
A 1 B A

(6)

Equations (2) (6) electronic problem

The electronic energy is not a constant but depends on the nuclear geometry (molecular
conformation). This geometry dependent electronic energy plays the role of the
potential energy in the Schrodinger equation for the nuclear motion and it is generally
termed potential energy surface (PES).
If the electronic problem is solved
we can solve for the motion of the nuclei using the electronic energy E(R) as
the potential energy in Schrdinger equation for the nuclear motion.
Since the electrons move much faster than the nuclei
we can replace the electronic coordinates by their average values (averaged
over the electronic wave-function)
Nuclear Hamiltonian
o

describes the motion of the nuclei in the average field of the electrons
N
N M
N 1 N
M 1 M
1
1
Z
1
Z Z
2A i2 A
A B
A 1 2 M A
i 1 2
i 1 A 1 riA
i 1 j i rij
A 1 B A RAB
M

H N

M 1 M
1
Z Z
2

A Ee ({R}) A B
A 1 2 M A
A 1 B A RAB
M

1
2A Etotpot ({R})
A 1 2 M A

M 1 M
1
Z Z
2A (r , R) H elec (r , R)dr A B
A 1 2 M A
A 1 B A RAB
r
M

HN= H N

The integral corresponds to the potential energy of nuclei in the field of electrons.

Potential energy surface (PES)

Etotpot ({R})

M. Oltean et al., Phys. Chem. Chem. Phys., 15 (2013) 13978-13990

 nuclear Schrdinger equation

HN|N> = E|N>
N - nuclear wavefunction
o

solution of the ro-vibrational problem for the nuclear coordinates, in the

presence of an electronic potential energy surface

o
E

describes the vibration, rotation and translation of a molecule

- total energy of the molecule (in the Born-Oppenheimer approximation)

- includes:

- electronic energy
- vibrational energy
- rotational energy
- translational energy

Total wave-function in the Born-Oppenheimer approximation:

(x,R) = e(x,{R})N(R)
Born-Oppenheimer approximation
-

usually a good approximation

bad approximation for:

o

excited states (high energy for the nuclear motion)

degenerate or cuasidegenerate states

Requirements for the wave function

We will assume the Born-Oppenheimer approximation and will only be concerned with
the electronic Schrdinger equation.
1. Normalization
For all quantum mechanical wave-function describing stationary states, is normalized
to unity.

(r )(r )dr 1

Integration is performed over the coordinates of all N electrons.

The wavefunction must also be single-valued, continuous and finite.
2. Antisymmetry with respect to the permutation of two electrons
Electrons are fermions and a many electron wave-function must be antisymmetric with
respect to the interchange of the coordinate x (both space and spin) of any two
electrons.
(x1, x2, ... , xi, ..., xj, ...,xN) = -(x1, x2, ... , xj, ..., xi, ...,xN)
The Pauli exclusion principle is a direct result of this antisymmetry principle.

3. The electronic wavefunctions must be eigenfunctions of Sz and S2 operators,

with the eigenvalues MS and S(S+1).
Since the electronic Hamiltonian does not contain any spin operators, it does commute
with the operators Sz and S2 defined below, with the corresponding eigenvalues MS and
S(S+1), respectively.

Sz

s zi MS

S2

2
i

S(S 1)

[H,S2]=0

[H,Sz]=0

We take care of spin by using spin-orbitals instead of pure spatial orbitals.

() and () spin functions (complete and orthonormal)

( ) ( )d ( ) ( )d 1
1
and

( ) ( )d ( ) ( )d 0
0
The electron is described by spatial (r) and spin () coordinates:
x={r,}

Homework
1.

Write

the

Z-matrix

for

the

tetramethylsilane

(TMS=Si(CH3)4) molecule in Td symmetry.

2. Use the Gaussian program and obtain the PES of the water molecule in the C 2v
symmetry by varying the bond length from 0.9 to 1.1 and the bond angle from 100o to
110o. Plot the PES using a dedicated software (GaussView, Mathematica, MathLab,
Mathcad).
3. Write

program

to

calculate

the

coordinates of the atoms in a graphene sheet

(10x10

atoms)

whose structure is given

below. The C-C bond length in graphene is

1.42.
The Nobel prize in physics for 2010 was awarded to Andre Geim and Konstantin Novoselov at the University of
Manchester "for groundbreaking experiments regarding the two-dimensional material graphene".