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to Hydrogen
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V=
4 r
2. Reduced Mass
Generally the mass of an e- (9.1 10-28 g)
is negligible when compared to the mass of
proton (1.76 10-24 g).
Due to this reason we may assume that the
mass of an electron is roughly equal to the
reduced mass of H atom.
mp . me
mp + me
mp . me
=
mp
= me
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The position of a
particle on the surface
of a sphere of radius r
is more conveniently
determined in terms of
two angular variables
(coordinates) - ,
called the azimuthal
angle and , called the
zenith angle.
The angle is the angle measured in the xy plane between the x axis
and the projection of the line r joining the particle, P with the centre
of the sphere. It varies from 0 to 2.
The angle is the angle measured between the line r and the z axis. It
varies from 0 to .
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
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Atomic Orbitals
For an atom, use Schrdingers equation
Find permissible energy levels for electrons around
nucleus.
For each energy level, the wave function defines an
orbital, a region where the probability of finding an
electron is high
The orbital properties of greatest interest are size,
shape (described by wave function) and energy.
Solution for multi-electron atoms is a very difficult
problem, and approximations are typically used
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
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n,l ,m r , , Rn,l r lm , ;
Rnl describes how wave function varies with
distance of electron from nucleus
Ylm describes the angular dependence of the wave
function
Subscripts n, l and m are quantum numbers of
hydrogen
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
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p orbital
d orbital
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s orbital:
l=0, m=0
p orbital:
l=1, m=-1,0,1
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
d orbital:
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l=2, m=-2,-1,0,1,2
Name
Allowed Values
principal
1,2,3..
quantum number
Any
number
ml
magnetic
-l ,- l+1,0,( l-1), 2 l +1
quantum number l
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
Allowed
States
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Shell (n)
Subshell symbol
1s
2
2
3
3
3
0
1
0
1
2
2s
2p
3s
3p
3d
0s
1p
2d
3-f
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Example
n
ml
Wave
Function
Subshell
symbol
Y1,0,0
1s
2
3
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Orbital shapes
Solution of the
Schrodinger wave equation
for a one electron atom :
1
1,0,0 r , , 3
ao
1
0,0 ,
4
1/ 2
1/ 2
r
exp
ao
2
10
ao
0
.
529
x
10
m
mke2
h
1.055 x10 34 Js
2
m mass of electron 9.109 x10 31 kg
k Coulomb' s constant 8.988 x109 Jm / Cb 2
e electron charge 1.602 x10 19 Cb
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Probability
Y1s2
Y1s
r
A spherical surface that
contains 90% of the total
electron probability
(orbital representation)
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
r90%
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Other orbitals
n
ml
Wave
Function
Subshell
symbol
Y1,0,0
1s
Y2,0,0
2s
-1
Y2,1,-1
2p
Y2,1,0
2p
Y2,1,1
2p
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me
En 2 2 2
8 o h n
m - mass of electron
e - electron charge
h Planck constant
permittivity of free space
Because n is restricted to integer values, energy levels are
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
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quantized
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Example
n
ml
Wave
Function
Subshell
symbol
Y1,0,0
1s
Y2,0,0
2s
-1
Y2,1,-1
2p
Y2,1,0
2p
Y2,1,1
2p
ms
(1/2), (-1/2)
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ml
Wave
Function
Subshell
symbol
Y1,0,0
1s
Y2,0,0
2s
-1
Y2,1,-1
2p
Y2,1,0
2p
Y2,1,1
2p
ms
(1/2), (-1/2)
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Example: Carbon
n
ml
Wave
Function
Subshell
symbol
Y1,0,0
1s
Y2,0,0
2s
-1
Y2,1,-1
2p
Y2,1,0
2p
Y2,1,1
2p
ms
(1/2), (-1/2)
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Nodes in orbitals: 2p
orbitals:
angular node that passes
through the nucleus
Orbital is dumb bell shaped
Important: the + and - that
is shown for a p orbital
refers to the mathematical
sign of the wavefunction, not
electric charge!
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
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Nodes in orbitals: 3d
orbitals:
two angular nodes that
passes through the
nucleus
Orbital is four leaf
clover shaped
d orbitals are important
for metals
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(spin down)
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Born-Oppenheimer Approximation
the nuclei are much heavier than the electrons and
move more slowly than the electrons
in the Born-Oppenheimer approximation, we freeze
the nuclear positions, Rnuc, and calculate the
electronic wavefunction, Yel(rel;Rnuc) and energy
E(Rnuc)
E(Rnuc) is the potential energy surface of the
molecule (i.e. the energy as a function of the
geometry)
on this potential energy surface, we can treat the
motion of the nuclei classically or quantum
mechanically
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
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Born-Oppenheimer Approximation
freeze the nuclear positions (nuclear kinetic energy is zero in
the electronic Hamiltonian)
H
el
electrons
2 2 electrons
i
2me
i
nuclei
e2 Z A electrons e2 nuclei e2 Z A Z B
riA
rij A B rAB
i j
*
Y
el Hel Yel d
*
Y
el Yel d
E depends on the nuclear positions through the nuclearelectron attraction and nuclear-nuclear repulsion terms
E = 0 corresponds to all particles at infinite separation
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
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Ytotal Yel nuc , H
nuc
nuc
nuc
H
nuc
nuclei
2
E (R nuc )
2m A
2
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Hartree Approximation
assume that a many electron wavefunction can be
written as a product of one electron functions
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Hartree-Fock Approximation
the Pauli principle requires that a wavefunction for electrons
must change sign when any two electrons are permuted
1 2 n
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Spin Orbitals
each spin orbital I describes the distribution of one electron
in a Hartree-Fock wavefunction, each electron must be in a
different spin orbital (or else the determinant is zero)
an electron has both space and spin coordinates
an electron can be alpha spin (, , spin up) or beta spin (, ,
spin down)
each spatial orbital can be combined with an alpha or beta
spin component to form a spin orbital
thus, at most two electrons can be in each spatial orbital
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Fock Equation
take the Hartree-Fock wavefunction
Y 1 2 n
put it into the variational energy expression
Evar
*
Y
HYd
*
Y
Yd
Evar / i 0,
i j d ij
F i ii
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
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Fock Equation
F i ii
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Fock Operator
V
J K
F T
NE
kinetic energy operator
2
2
T
2me
V
ne
nuclei
e2 Z A
riA
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Fock Operator
V
J K
F T
NE
Coulomb operator (electron-electron repulsion)
electrons
J i {
e2
j rij j d }i
exchange operator (purely quantum mechanical arises from the fact that the wavefunction must
switch sign when you exchange to electrons)
electrons
{
K
i
e2
j rij i d } j
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
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1.
2.
3.
4.
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Hartree-Fock Orbitals
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Hartree-Fock Orbitals
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LCAO Approximation
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Basis Functions
c
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Roothaan-Hall Equations
Evar
*
Y
HYd
*
Y
Yd
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Roothaan-Hall Equations
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Fock matrix
F F d
overlap matrix
S d
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V
) d
h (T
ne
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Summary
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