Basis Set

Goal: select the most accurate calculation that is

computationally feasible for a given molecular system
Model chemistry: theoretical method and basis set
HF MP2 CCSD CCSD(T) CCSDT

Full CI
Minimal

Split-
valence

Polarized

Diffuse

High
angular
momentum




Exact
solution
Model Chemistries - three areas
of consideration
Basis sets
Theoretical methods
Basis set
Basis functions approximate orbitals of
atoms in molecule
Linear combination of basis functions
approximates total electronic
wavefunction
Basis functions are linear combinations
of gaussian functions
Contracted gaussians
Primitive gaussians

Slater-type orbitals (J.C. Slater)

Represent electron density well in valence
region and beyond (not so well near nucleus)
Evaluating these integrals is difficult
Gaussian-type orbitals (F. Boys)

Easier to evaluate integrals, but dont
represent electron density well
Overcome this by using linear combination of
GTOs

STOs v. GTOs

g o, r
( )
= cx
n
y
m
z
l
e
or
2

_

= d
p
g
p
p

s(,, r ) =cx
n
y
m
z
l
e
,r
Minimal basis set
One basis function for every atomic
orbital required to describe the free
atom
Most-common: STO-3G
Linear combination of 3 Gaussian-type
orbitals fitted to one Slater-type orbital
CH
4
: H(1s); C(1s,2s,2p
x
,2p
y
,2p
z
)
More basis functions per atom
Split valence basis sets
Double-zeta: 2 sizes of basis functions
for each valence atomic orbital
3-21G CH
4
: H(1s,1s'),
C(1s,2s,2s',2p
x
,2p
y
,2p
z
,2p
x
',2p
y
',2p
z
')
Triple-zeta: 3 sizes of basis functions
for each valence atomic orbital
6-311G CH
4
: H(1s,1s',1s''),

C(1s,2s,2s',2s'',2p
x
,2p
y
,2p
z
, 2p
x
',2p
y
',2p
z
',2p
x
'',2p
y
'',2p
z
'')
More basis functions per atom
Split valence basis sets
Double-zeta:

Triple-zeta:

36
22
Total
42 22
Total
Ways to increase a basis set
Add more basis functions per atom
allow orbitals to change size
Add polarization functions
allow orbitals to change shape
Add diffuse functions for electrons with
large radial extent
Add high angular momentum functions
Add polarization functions
Allow orbitals to change shape
Add p orbitals to H
Add d orbitals to 2nd row atoms
Add f orbitals to transition metals
6-31G(d) - d functions per heavy atoms
Also denoted: 6-31G*
6-31G(d,p) - d functions per heavy
atoms and p functions to H atoms
Also deonoted: 6-31G**
Add diffuse functions
Large s and p orbitals for diffuse electrons
Lone pairs, anions, excited states, etc.
6-31+G - diffuse functions per heavy atom
6-31++G - diffuse functions both per heavy
atom and per H atom
High angular momentum functions
Custom-made basis sets
6-31G(2d) - 2d functions per heavy atom
6-311++G(3df,3pd)

Triple-zeta valence
Diffuse functions on heavy atoms, H atoms
3d, 1f functions per heavy atom; 3p, 1d
functions per H atom

Minimal basis sets
A common naming convention for minimal basis sets is STO-XG, where X is an integer.
This X value represents the number of Gaussian primitive functions comprising a single basis function.
In these basis sets, the same number of Gaussian primitives comprise core and valence orbitals.
Minimal basis sets typically give rough results that are insufficient for research-quality publication,
but are much cheaper than their larger counterparts. Here is a list of commonly used minimal basis sets:


STO-2G
STO-3G
STO-6G
STO-3G* - Polarized version of STO-3G

Split-valence basis sets
During most molecular bonding, it is the valence electrons which principally take part in the bonding. In recognition of this fact,
it is common to represent valence orbitals by more than one basis function, (each of which can in turn be composed of a fixed
linear combination of primitive Gaussian functions). The notation for these split-valence basis sets is typically X-YZg.
In this case, X represents the number primitive Gaussians comprising each core atomic orbital basis function.
The Y and Z indicate that the valence orbitals are composed of two basis functions each
Here is a list of commonly used split-valence basis sets:
3-21g
3-21g* - Polarized
3-21+g - Diffuse functions
3-21+g* - With polarization and diffuse functions
6-31g
6-31g*
6-31+g*
6-31g(3df, 3pd)
6-311g
6-311g*
6-311+g*
SV(P)
SVP

Double, triple, quadruple zeta basis sets
Basis sets in which there are multiple basis functions corresponding to each atomic orbital,
including both valence orbitals and core orbitals or just the valence orbitals, are called double, triple,
or quadruple-zeta basis sets. Here is a list of commonly used multiple zeta basis sets:
multiple zeta basis sets:
cc-pVDZ - Double-zeta
cc-pVTZ - Triple-zeta
cc-pVQZ - Quadruple-zeta
cc-pV5Z - Quintuple-zeta, etc.
aug-cc-pVDZ, etc. - Augmented versions of the
preceding basis sets with added diffuse functions
TZVPP - Triple-zeta
QZVPP - Quadruple-zeta