Application of SWE To H Like System

Application of S.W.E.
to Hydrogen
& Hydrogen Like Systems
Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,
Dr. D. Ilangeswaran, M. Sc., M. Phil., Ph. D.,
Assistant Professor of Chemistry

Rajah Serfoji Govt. College
(Autonomous)
Thanjavur - 613005
Hydrogen Like Atom

A system with a central nucleus and an
electron is known as H like atom.
In such systems the nucleus & the electron
are held together by means of electrostatic
attraction.
The wave function for either the H or H
like atoms (i.e. one e- systems) like He+, Li2+
can be calculated accurately.
The SWE for H atom

1. Potential energy
In H atom, the +vely charged proton is at the
centre whereas the vely charged e- is at a
distance, r from the nucleus.
The potential energy of attraction between
the nucleus & the e- is given in equation (1).
Where 40 is the permitivity, in atomic unit = 1.
SI unit of it is 1.1126 10-10 C2 m-1 J-1.
and Z = 1 for H atom.
-Z e2
(1)
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
5
The SWE for H & H like atom is
Using the values of m & V in this equation we get
Transforming the above equation from Cartesian

coordinate to polar coordinates (r, , ), we get
Equation (4) involves three variables, r, , and .

Where is the zenith angle and is azimuthal
angle.
Separation of variables
The dependence of r, , and occur in
different terms of the above equation. Since the r
term involves the potential energy, it is possible
to separate the partial differential equations, one
in each of the variables.
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 .
The above mentioned variables can be separated by inserting into

equation (3) a solution of the form
(r, , ) = R(r), Y(), Z()
Where R, Y and Z are functions of only three variables r, and
respectively.
The function R(r) is referred to as the radial function since it
describes how the wave function varies with the radial distance, r.
The functions Y() and Z() combined together as say
Y(,) represents angular part of the wave function.
The following necessary derivatives can be obtained by
proper differentiation.
10
Since the two sides of equation (7) are functions of different

variables, this equation can be correct, only if each side of this
equation is equal to the same constant, say m2.
Dividing equation (9) by sin2
11
12
13
Thus equation (4) is now separated into three ordinary

differential equations (8), (13) and (14) each of which involves
only one variable. These equations are called as , r and
equations respectively.
14
15
16
17
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
18
The hydrogen atom

The electron of the hydrogen atom moves in three
dimensions and has potential energy (attraction to
positively charged nucleus)
The Schrodinger equation can be solved to find
the wave functions associated with the hydrogen
atom
In 1-D particle in a box, the wave function is a
function of one quantum number; the 3-D
hydrogen atom is a function of three quantum
numbers
19
Wave functions of hydrogen

The solution of the Schrodinger equation
for the hydrogen atom is:
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
20
Principal quantum number, n

Has integral values of 1,2,3 and is related
to size and energy of the orbital
As n increases, the orbital becomes larger and
the electron is farther from the nucleus
As n increases, the orbital has higher energy
(less negative) and is less tightly bound to the
nucleus
21
Angular quantum number, l

Can have values of 0 to n-1 for each
value of n and relates to the angular
momentum of the electron in an orbital
The dependence of the wave function
on l, determines the shape of the orbitals
The value of l, for a particular
orbital is commonly assigned a
s orbital
letter:
0s
1p
2d
3f
p orbital
d orbital
22
Magnetic quantum number, ml

Can have integral values between l and - l, including
zero and relates to the orientation in space of the
angular momentum.
s orbital:
l=0, m=0
p orbital:
l=1, m=-1,0,1
d orbital:
23
l=2, m=-2,-1,0,1,2
Calculation of quantum numbers

Quantum
Numbers
Name
Allowed Values
principal
1,2,3..
quantum number
Any
number
Angular quantum 0,1,2,(n-1)

number
ml
magnetic
-l ,- l+1,0,( l-1), 2 l +1
quantum number l
Allowed
States
24
Shells and subshells

All states with the same principal quantum number are
said to form a shell; the states having specific values of
both n and l are said to form a subshell
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
25
Example
n
ml
Wave
Function
Subshell
symbol
Y1,0,0
1s
2
3
26
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
27
Electron probability distribution

Wave function
Probability
Y1s2
Y1s
r
A spherical surface that
contains 90% of the total
electron probability
(orbital representation)
r90%
28
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
29
Allowed energies of hydrogen

The energy En of the wave function Ynlm depends only on
n:
4
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
30
quantized
Atomic Orbitals: Multi-electron atoms

Electron spin quantum number, ms
This quantum number only has two values: and .
This means that the electron has two spin states, thus
producing two oppositely directed magnetic moments
This quantum number doubles the number of allowed states
for each electron.
Pair of electrons in a given orbital must have opposite spins
31
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)
32
Pauli exclusion principle

No two electrons can have the same set of quantum
numbers: n, l, ml and ms
Aufbau principle
Electrons fill in the orbitals of successively increasing
energy, starting with the lowest energy orbital
Hunds rule
For a given shell (example, n=2), the electron occupies
each subshell one at a time before pairing up
33
Orbital energies: multi-electron atoms

Energy depends on both n and l
34
Example: Nitrogen (1s22s22p3)

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)
35
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)
36
Atomic Orbitals: Summary

In the quantum mechanical model, the electron is
described as a wave. This leads to a series of wave
functions (orbitals) that describe the possible energies
and spatial distribution available to the electron
The orbitals can be thought of in terms of probability

distributions (square of the wave function)
37
Sizes, Shapes, and orientations of orbitals

n determines size; l determines shape
ml determines orientation
38
Nodes in orbitals: s orbitals: 1s no nodes, 2s one node,

3s two nodes
39
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!
40
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
41
The fourth quantum number: Electron Spin

ms = +1/2 (spin up) or -1/2 (spin down)
Spin is a fundamental property of electrons, like its

charge and mass.
(spin up)
(spin down)
42
Electrons in an orbital must have different values of

ms
This statement demands that if there are two
electrons in an orbital one must have ms = +1/2 (spin
up) and the other must have ms = -1/2 (spin down)
This is the Pauli Exclusion Principle
An empty orbital is fully described by the three
quantum numbers: n, l and ml
An electron in an orbital is fully described by the
four quantum numbers: n, l, ml and ms
43
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
44
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
calculate the electronic wavefunction and energy

Y EY , E
H
el el
el
*
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
45
Nuclear motion on the

Born-Oppenheimer surface
Classical treatment of the nuclei (e,g. classical
trajectories)
F ma, F E / R nuc , a 2 R nuc / t 2

Quantum treatment of the nuclei (e.g. molecular
vibrations)

Ytotal Yel nuc , H
nuc
nuc
nuc

H
nuc
nuclei
2
E (R nuc )
2m A
2
46
Hartree Approximation
assume that a many electron wavefunction can be
written as a product of one electron functions
Y (r1 , r2 , r3 ,) (r1 ) (r2 ) (r3 )

if we use the variational energy, solving the many
electron Schrdinger equation is reduced to
solving a series of one electron Schrdinger
equations
each electron interacts with the average
distribution of the other electrons
47
Hartree-Fock Approximation
the Pauli principle requires that a wavefunction for electrons
must change sign when any two electrons are permuted
since |Y(1,2)|2=|Y(2,1)|2, Y(1,2)=Y(2,1) (minus sign for fermions)
the Hartree-product wavefunction must be antisymmetrized

can be done by writing the wavefunction as a determinant
determinants change sign when any two columns are switched
1 (1) 1 (2) 1 (n)

1 2 (1) 2 (2) 2 (n)
n
n (1) n (1) n (n)
1 2 n
48
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
49
Fock Equation
take the Hartree-Fock wavefunction
Y 1 2 n
put it into the variational energy expression
Evar
*
Y
HYd
*
Y
Yd
minimize the energy with respect to changes in the orbitals while

keeping the orbitals orthonormal
Evar / i 0,
i j d ij
yields the Fock equation
F i ii
50
Fock Equation
F i ii
the Fock operator is an effective one electron

Hamiltonian for an orbital
is the orbital energy
each orbital sees the average distribution of all the
other electrons
finding a many electron wavefunction is reduced to
finding a series of one electron orbitals
51
Fock Operator
V
J K
F T
NE
kinetic energy operator
2
2
T
2me
nuclear-electron attraction operator

V
ne
nuclei
e2 Z A
riA
52
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
53
Solving the Fock Equations

F i ii
1.
2.
3.
4.
obtain an initial guess for all the orbitals i

use the current I to construct a new Fock operator
solve the Fock equations for a new set of I
if the new I are different from the old I, go back to
step 2.
54
Hartree-Fock Orbitals
for atoms, the Hartree-Fock orbitals can be computed

numerically
the s resemble the shapes of the hydrogen orbitals
s, p, d orbitals
radial part somewhat different, because of interaction with

the other electrons (e.g. electrostatic repulsion and
exchange interaction with other electrons)
55
Hartree-Fock Orbitals
for homonuclear diatomic molecules, the

Hartree-Fock orbitals can also be computed
numerically (but with much more difficulty)
the s resemble the shapes of the H2+ orbitals
, , bonding and anti-bonding orbitals
56
LCAO Approximation
numerical solutions for the Hartree-Fock orbitals

only practical for atoms and diatomics
diatomic orbitals resemble linear combinations of
atomic orbitals
e.g. sigma bond in H2
1sA + 1sB
for polyatomics, approximate the molecular orbital
by a linear combination of atomic orbitals (LCAO)
57
Basis Functions
c
s are called basis functions

usually centered on atoms
can be more general and more flexible than atomic
orbitals
larger number of well chosen basis functions yields
more accurate approximations to the molecular
orbitals
58
Roothaan-Hall Equations
choose a suitable set of basis functions
plug into the variational expression for the energy
Evar
*
Y
HYd
*
Y
Yd
find the coefficients for each orbital that minimizes

the variational energy
59
Roothaan-Hall Equations
basis set expansion leads to a matrix form of the

Fock equations
F Ci = i S Ci
F Fock matrix
Ci column vector of the molecular orbital
coefficients
I orbital energy
S overlap matrix
60
Fock matrix and Overlap matrix
Fock matrix
F F d
overlap matrix
S d
61
Intergrals for the Fock matrix
Fock matrix involves one electron integrals of kinetic and

nuclear-electron attraction operators and two electron
integrals of 1/r
V
) d
h (T
ne
one electron integrals are fairly easy and few in number

(only N2)
1
( | ) (1) (1) (2) (2)d 1d 2
r12
two electron integrals are much harder and much more
numerous (N4)
62
Solving the Roothaan-Hall Equations

1. choose a basis set
2. calculate all the one and two electron integrals
3. obtain an initial guess for all the molecular orbital
coefficients Ci
4. use the current Ci to construct a new Fock matrix
5. solve F Ci = i S Ci for a new set of Ci
6. if the new Ci are different from the old Ci, go back to
step 4.
63
Solving the Roothaan-Hall Equations
also known as the self consistent field (SCF) equations, since

each orbital depends on all the other orbitals, and they are
adjusted until they are all converged
calculating all two electron integrals is a major bottleneck,
because they are difficult (6 dimensional integrals) and very
numerous (formally N4)
iterative solution may be difficult to converge
formation of the Fock matrix in each cycle is costly, since it
involves all N4 two electron integrals
64
Summary
start with the Schrdinger equation

use the variational energy
Born-Oppenheimer approximation
Hartree-Fock approximation
LCAO approximation
65
The Pauli principle and Slater determinants
66
67
68
69

Application of SWE To H Like System

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Application of S.W.E.

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M. Sc., M. Phil., Ph. D.,

Assistant Professor of Chemistry

Hydrogen Like Atom

The SWE for H atom

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

The SWE for H & H like atom is

Using the values of m & V in this equation we get

Transforming the above equation from Cartesian

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Equation (4) involves three variables, r, , and .

The above mentioned variables can be separated by inserting into

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Since the two sides of equation (7) are functions of different

Dividing equation (9) by sin2

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Thus equation (4) is now separated into three ordinary

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

The hydrogen atom

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Wave functions of hydrogen

Principal quantum number, n

Angular quantum number, l

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Magnetic quantum number, ml

Calculation of quantum numbers

Angular quantum 0,1,2,(n-1)

Shells and subshells

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Electron probability distribution

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Allowed energies of hydrogen

Atomic Orbitals: Multi-electron atoms

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Pauli exclusion principle

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Orbital energies: multi-electron atoms

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Example: Nitrogen (1s22s22p3)

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Atomic Orbitals: Summary

The orbitals can be thought of in terms of probability

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Sizes, Shapes, and orientations of orbitals

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Nodes in orbitals: s orbitals: 1s no nodes, 2s one node,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,

The fourth quantum number: Electron Spin

Spin is a fundamental property of electrons, like its

Dr. D. Ilangeswaran, M.Sc., M.Phil., Ph.D.,