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and Hartree-Fock theory

Video
III.iv

Constructing a 1-Electron Wave Function

The units of the wave function are such that its square is electron per

volume. As electrons are quantum particles with non-point distributions,

sometimes we say density or probability density instead of electron per

volume (especially when there is more than one electron, since they are

indistinguishable as quantum particles)

For instance, a valid wave function in cartesian coordinates for one electron

might be:

2Z 5 / 2 % 2 2 2 ( $Z x 2 +y 2 +z 2 / 3

"( x, y, z; Z ) = ' 6 $ Z x + y + z * ye

81 # & )

factor factor directionality square

(if any) integrability

Constructing a 1-Electron Wave Function

A valid wave function in cartesian coordinates for one electron might be:

2Z 5 / 2 % 2 2 2 ( $Z x 2 +y 2 +z 2 / 3

"( x, y, z; Z ) = ' 6 $ Z x + y + z * ye

81 # & )

factor factor directionality square

(if any) integrability

probability of finding the electron

x1 x x 2 within a particular cartesian volume

x2 y2 z2 2 element (normalization factors are

P y1 y y 2 =

x1 y1 z1

dx dy dz determined by requiring that P = 1

when all limits are infinite, i.e.,

z1 z z 2

integration over all space)

Constructing a 1-Electron Wave Function

To permit additional flexibility, we may take our wave function to be a linear

combination of some set of common basis functions, e.g., atomic orbitals

(LCAO). Thus

N

( r ) = a ( r)

i

i=1

For example, consider the wave

function for an electron in a CH bond. C

It could be represented by s and p

functions on the atomic positions, or s

functions along the bond axis, or any

other fashion convenient. H

Constructing a 1-Electron Wave Function

To optimize the coefficients in our LCAO expansion, we use the variational

principle, which says that

a i i H a j j dr

a a H

i j i j dr a a i j H ij

i j ij ij

E= = =

a a i j i j dr a a i j S ij

a i i a j j dr

ij ij

i j

other roots are excited states)each value of E that satisfies the

secular equation determines all of the ai values and thus the shape

of the molecular orbital wave function (MO)

H21 ES21 H22 ES22 H2 N ES2 N

= 0

HN1 ESN1 H N2 ES N2 HNN ESNN

What Are These Integrals H?

The electronic Hamiltonian includes kinetic energy, nuclear attraction, and, if

there is more than one electron, electron-electron repulsion

nuclei electrons 2

1 Zk

H ij = i 2 j i

2

rk

j + i rn

j

k n

many-body problem that has not been solved even for classical

particles. An approximation is to ignore the correlated motion of the

electrons, and treat each electron as independent, but even then, if

each MO depends on all of the other MOs, how can we determine

even one of them? The Hartree-Fock approach accomplishes this

for a many-electron wave function expressed as an

antisymmetrized product of one-electron MOs (a so-called Slater

determinant)

Choose a basis set

Compute and store all overlap,

Fock procedure

one-electron, and two-electron Guess initial density matrix P(0)

integrals

Fock secular equation

F11 ES11 F12 ES12 F1N ES1N

Replace P(n1) with P(n) occupied MOs F21 ES21 F22 ES22 F2 N ES2 N

= 0

Is new density matrix P(n) FN1 ES N1 FN2 ES N2 FNN ESNN

no

sufficiently similar to old

Choose new geometry density matrix P(n1) ?

1 nuclei 1

according to optimization

algorithm yes

F = 2 Zk

2 k rk

Optimize molecular geometry?

1

no

yes no

+ P ( ) ( )

2

Does the current geometry occupied

Output data for

satisfy the optimization

criteria? unoptimized geometry P = 2 ai ai

i

yes 1

( ) = (1) (1) r12

( 2) (2)dr (1)dr (2)

Output data for optimized

geometry One MO per root E

Cement Your Understanding

1 nuclei 1

F = 2 Zk

2 k rk

1

+ P ( ) ( )

2

mathematical notation, every generic integral in the

Fock matrix for Slater-type orbital basis functions with

all functions and operators expressed in Cartesian

coordinates (which is how they are most typically

evaluated in actual practice)

Semiempirical

Molecular Orbital Theory

Semiempirical
simplica:ons

of
the
Fock
matrix
(early)

Video
III.v

Choose a basis set

Compute and store all overlap,

Fock procedure

one-electron, and two-electron Guess initial density matrix P(0)

integrals

Fock secular equation

F11 ES11 F12 ES12 F1N ES1N

Replace P(n1) with P(n) occupied MOs F21 ES21 F22 ES22 F2 N ES2 N

= 0

Is new density matrix P(n) FN1 ES N1 FN2 ES N2 FNN ESNN

no

sufficiently similar to old

Choose new geometry density matrix P(n1) ?

1 nuclei 1

according to optimization

algorithm yes

F = 2 Zk

2 k rk

Optimize molecular geometry?

1

no

yes no

+ P ( ) ( )

2

Does the current geometry occupied

Output data for

satisfy the optimization

criteria? unoptimized geometry P = 2 ai ai

i

yes 1

( ) = (1) (1) r12

( 2) (2)dr (1)dr (2)

Output data for optimized

geometry One MO per root E

nuclei occupied

1 2 1

F = Zk P = 2 ai ai

2 k rk i

1

+ P ( ) ( )

2 i = a

i

F21 ES21 F22 ES22 F2N ES2N

= 0

FN1 ES N1 FN2 ES N2 FNN ESNN

Consider only rst- and second-row atoms; consider a minimal basis set

1

( ) = (1) (1) r ( 2) ( 2) dr1dr2

12

nuclei occupied

1 2 1

F = Zk P = 2 ai ai

2 k rk i

1

+ P ( ) ( )

2 i = a i

1

( ) = (1) (1) r ( 2) ( 2) dr1dr2

12

Things
to
consider
in
a
semiempirical
model:

1) What
shall
I
choose
for
a
basis
set?

2) What
shall
I
do
for
overlap
integrals
(in
the
secular
determinant)?

3) What
shall
I
do
for
Fock
matrix
elements?

4) As
part
of
(3),
what
shall
I
do
about
electron
repulsion
integrals?

Essen:ally
all
semiempirical
models
adopt
a
minimal
basis
set.
The
AO
basis

func:ons
cover
only
the
valence
s,
p,
d,
and
f
orbitals
(p,
d,
and
f
only
as
needed),

one
func:on
per
orbital
(so,
1
s,
3
p,
5d,
and
7f
orbitals).
The
basis
func:ons

themselves
are
taken
to
be
Slater
orbitals.
n +1/ 2

STO ( r, , ;,n,l,m) =

( 2) n 1 r m

e Yl ( , )

1/ 2 r

[(2n)!]

nuclei occupied

1 2 1

F = Zk P = 2 ai ai

2 k rk i

1

+ P ( ) ( )

2 i = a i

1

( ) = (1) (1) r ( 2) ( 2) dr1dr2

12

The overlap between any two STOs can be computed analy:cally (i.e., it is a simple

arithme:c func:on of posi:on and values of , n, l, and m). Overlap integrals nd

use in compu:ng some Fock matrix elements.

adopted.

n +1/ 2

STO ( r, , ;,n,l,m) =

( 2)

r n 1e rYlm ( , )

1/ 2

[(2n)!]

nuclei occupied

1 2 1

F = Zk P = 2 ai ai

2 k rk i

1

+ P ( ) ( )

2 i = a

i

1

( ) = (1) (1) r ( 2) ( 2) dr1dr2

12

A Fock matrix element can be diagonal (i.e., = ), or not. When the matrix

element is o-diagonal, it can be monatomic (i.e., , but and are on the

same atom), or it can be diatomic (the only remaining possibility)

As
every
Fock
matrix
element
includes
ERIs,
rst
lets
consider
the
ERIs
(well
get
to

one-electron
integrals
later)

COMPLETE
NEGLECT
OF
DIFFERENTIAL
OVERLAP

1

Reducing
the
N
scaling
problem:

4

( ) = (1) (1)

r

( 2) ( 2) dr dr 1 2

12

integrals between 2 AO basis func:ons, which

may or may not be on the same atom

the atoms A and B on which and are

found, respec:vely.

AA = IPA EAA interac:on between electrons on same atom

taken as dierence between ioniza:on

poten:al and electron anity

one extra e-e repulsion

AA + BB IP on atom M

AB =

2 + rAB ( AA + BB )

M + M M + M

func:on above has proper limits at rAB = 0

(since then A must be B, the same atom)

and at rAB very large ( just 1/rAB, which is EA

Coulombs law in atomic units)

COMPLETE NEGLECT OF DIFFERENTIAL OVERLAP

1

Reducing the N scaling problem:

4

( ) = (1) (1)

r

( 2) ( 2) dr dr

1 2

12

integrals between 2 AO basis func:ons, which

may or may not be on the same atom

the atoms A and B on which and are

found, respec:vely.

!CC !NN

H H

H H H : : H

C !CC C

!NN

N N

H : H :

H H H H

Semiempirical

Molecular
Orbital
Theory

Semiempirical
simplica:ons

of
the
Fock
matrix
(subsequent)

Video
III.vi

COMPLETE
NEGLECT
OF
DIFFERENTIAL
OVERLAP

1

Reducing
the
N
scaling
problem:

4

( ) = (1) (1)

r

( 2) ( 2) dr dr

1 2

12

integrals between 2 AO basis func:ons, which

may or may not be on the same atom

the atoms A and B on which and are

found, respec:vely.

!CC

H H

C !CC C

H H

INTERMEDIATE
NEGLECT
OF
DIFFERENTIAL
OVERLAP

1

Reducing
the
N
scaling
problem:

4

( ) = (1) (1)

r

( 2) ( 2) dr dr 1 2

12

same atom

( ss ss) = G ss

For an atom with only s and p valence

( ss pp) = G sp func:ons, 5 unique integrals are kept (they are

simply values, in energy units, that can be

( pp pp) = G pp

determined from spectroscopy or taken as

( pp p p) = G pp free parameters). Note that p refers to a p

orbital dierent from a reference one, e.g.,

( sp sp) = L sp

( pp | pp ) might be (pxpx | pypy ), i.e., the

through-space repulsive interac:on between

electrons in two perpendicular p orbitals

This
extra
exibility
in
the
atomic
ERIs
tends
to
improve
rela:ve
energies

for
electronic
states
that
dier
by
occupa:on
of
orbitals
on
single-centers.

That
is,
for
instance,
excited
states
that
are
well
characterized
as
one-

electron
local
excita:ons.
INDO
s:ll
nds
substan:al
use
for
spectroscopy.

NEGLECT
OF
DIATOMIC
DIFFERENTIAL
OVERLAP

1

Reducing
the
N
scaling
problem:

4

( ) = (1) (1)

r

( 2) ( 2) dr dr

1 2

12

where both and are on the same atom,

( ss ss) = Gss and and are on the same atom, but

neither the two atoms need to be the same,

( ) sp

ss pp = G nor do the two func:ons on the individual

( pp pp) = Gpp atoms need to be the same. For monatomic

ERIs, the INDO-like values are retained. For

( pp p p) = Gpp diatomic ERIs, there are 100 possible integrals

( sp sp) = Lsp for s and p basis func:ons (try and verify

that)

The
diatomic
integrals
are
not
easily
evaluated
for
Slater
type
orbitals.

Instead,
NDDO
methods
model
the
integrals
as
classical
mul:pole

interac:ons
between
the
two
atoms.
Whether
the
mul:pole
is
a
point

charge
(ss),
a
dipole
(sp),
or
a
quadrupole
(pp
or
pp)
depends
on
the

nature
of
the
orbitals,
and
the
orienta:on
of
the
higher
mul:poles
does,

too.
The
magnitudes
of
the
dipoles
and
quadrupoles
depend
on
the

exponents
of
the
Slater
basis
func:ons.

ONE-ELECTRON
INTEGRALS

nuclei

1 2 1

Zk

2 k

rk

1 2 1 nuclei

1

Zk Zk

2 rk k k

rk

nuclei

= U Z ( s s )

k k k

k k

an electron in atomic orbital and the alrac:on to a nucleus at the posi:ons of

other atoms k is Zk :mes the repulsion with an electron in an s orbital on the same

atom.

ONE-ELECTRON INTEGRALS

nuclei

1 2 1

Zk

2 k

rk

1 2 1 nuclei

1

Zk Zk

2 rk k k

rk

nuclei

= Z ( s s )

k k k

k k

where
the
rst
two
terms
are
zero
for
s
and
p
orbitals
by
symmetry
considera:ons

and
the
alrac:on
to
a
nucleus
at
the
posi:ons
of
other
atoms
k
is
Zk
:mes
the

repulsion
with
an
electron
in
an
s
orbital
on
the
same
atom.

ONE-ELECTRON
INTEGRALS

nuclei

1 2 1

Zk

2 k

rk

( + )S

=

2

where
is
our
old
friend
from
Hckel
theory,
the
resonance
integral
(a
numerical

parameter)
and
S
is
the
overlap
matrix
computed
from
the
Slater
type
orbitals.

Note
that
the
values
depend
on
both
the
atomic
number
and
the
orbital
(i.e.,

carbon
has
a
dierent
value
for
an
s
orbital
than
for
a
p
orbital)

Semiempirical

Molecular Orbital Theory

Semiempirical
parameteriza:ons

and
modern
usage

Video
III.vii

Big
Personali:es

FINAL MOLECULAR-MECHANICS-LIKE TOUCHUP

First adopted in MNDO, later in AM1 and PM3, etc.

VN ( A,B) = Z A Z B sA sA sBsB ( )

Z A Z B 4 b A,i ( rAB c A,i )

2

b B,i ( rAB c B,i )

2

+

rAB i=1

aA,ie + aB,ie

where
the
rst
term
says
that
nuclei
repel
each
other
propor:onal
to
the
degree

that
their
s
electrons
repel
one
another,
but
the
following
sum
eec:vely
creates

gaussian
shaped
ripples,
posi:ve
or
nega:ve,
in
the
poten:al
energy
surface

surrounding
the
atoms.
Such
an
approach
permits
a
ne
tuning
of
atomic

separa:ons
that
must
be
considered
rather
ad
hoc,
but
not
necessarily

inconsistent
with
semiempirical
principles.
(Later
extended
by
Jorgensen
and
co-

workers
using
Pairwise
Distance
Directed
Gaussians
(PDDG)
for
MNDO
and

PM3.)

Chemical
Intui:on
vs
Maths

Observables Occurrences 2 1 / 2

Z =

( )

calci, j expt i, j

wi2

i j

MNDO MNDO

AM1 AM1

PM3

AMPAC MOPAC

Errors in Computed Heats of Forma:on (kcal/mol)

MODERN USAGE? SPECIFIC RANGE PARAMETERS

Parameter AM1 AM1-SRP

H H

O

C C O + H + H2

H H C

Us 52.03 49.85 H H2O H H

Up 39.61 40.34

!s 15.72 16.91

!p 7.72 9.19

O

Us 97.83 99.18

Up 78.26 80.76

!s 29.27 29.00

!p 29.27 29.25

AM1-SRP 4.9 104.4 109.4

Expt. 5.1 104.4 109.5

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