Session 2
Basis Sets
CCCE 2008
Session 2: Basis Sets
Two of the major methods
(ab initio and DFT) require
some understanding of basis
sets and basis functions
This session describes the
essentials of basis sets:
What they are
How they are constructed
How they are used
Significance in choice
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Running a Calculation
In performing ab initio and DFT computational chemistry calculations, the chemist has
to make several decisions of input to the code:
The molecular geometry (and spin state)
The basis set used to determine the wavefunction
The properties to be calculated
The type(s) of calculations and any accompanying
assumptions
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Running a calculation
For ab initio or DFT
calculations, many
programs require a basis set
choice to be made
The basis set is an approximate representation of the
atomic orbitals (AOs)
The program then calculates
molecular orbitals (MOs)
using the Linear Combination of Atomic Orbitals
(LCAO) approximation
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Computational Chemistry Map
Chemist Decides:
Computer calculates:
Starting Molecular
Geometry
AOs
Basis Set (with
ab initio and DFT)
Type of Calculation
(Method and
Assumptions)
Properties to
be Calculated
AOs determine the
wavefunction ()
O
H
LCAO
O
H
MOs
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Critical Choices
Choice of the method (and basis set) used is
critical
Which method?
Molecular Mechanics, Ab initio, Semiempirical, or
DFT
Which approximation?
MM2, MM3, HF, AM1, PM3, or B3LYP, etc.
Which basis set (if applicable)?
Minimal basis set
Split-valence
Polarized, Diffuse, High Angular Momentum, ......
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Why is Basis Set Choice Critical?
The basis set needs to be able to approximate
the actual wave function sufficiently well to
give chemically meaningful results
Also needs a reasonable computational cost
Integrals should be evaluated quickly and
accurately
Trade-offs
Choice always involves a balance between
accuracy and computational cost
More accurate methods using larger basis sets will
take more computer time
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Theoretical Models
Goal of computational chemistry is to
mathematically represent chemical reality
Improving the basis set and the degree of electron
correlation improves the ability of the
computational model to approach reality
Ultimate goal is an exact solution of the
Schrdinger equation
CCCE 2008
Comparison of Some Methods for Accuracy
DFT Location??
HF
B
A
S
I
S
S
E
T
Minimal
STO-3G
Split Valence
3-21G
Polarized
6-31G(d)
6-311G(d,p)
MP2
MP3
MP4 QCISD(T) ...
Full CI
Electron Correlation
Diffuse
6-311+G(d,p)
High
ang.
Momentum
6-311+G(2d,p)
6-311++G(3df,3dp)
........
HF
Limit
Schrdinger
Equation
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Possible Basis Functions
1. Hydrogen-like Orbitals
Derived for a one-electron atom
Not truly accurate for a many-electron atom
Form:
( r , , ) = R( r )Yl m ( , )
R( r ) = radial function
Yl m = spherical harmonic
+ Advantages: Mutually orthogonal
Disadvantages: Complex form is awkward for
calculations; Most atoms of interest > one
electron
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Possible Basis Functions
True wavefunction should be antisymmetric to
electron interchange use spin orbitals
Antisymmetric linear combination of products of
spin orbitals used in an SCF calculation
HF-SCF calculation
Numerical methods were originally used to solve and
find the Hartree-Fock orbitals
Roothaan: Represent the HF orbitals as linear
combinations of a set of known (basis) functions
Commonly used set of basis functions for atomic HF
calculations is the set of Slater-type orbitals (STOs)
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Possible Basis Functions
2. Slater Type Orbitals (STOs)
Normalized form:
( 2 / a0 ) n + 0.5 ( n 1) ( r / a0 ) m
r
e
Yl ( , )
[( 2n )!]0.5
where n, m, and l are integers and (orbital
exponent) is a variational parameter
( r , , ) =
Improve results by using a linear combination of
several STOs to represent each HF orbital
HF-SCF atomic calculations require lots of
computation
Hartree did this numerically in the 1930s
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Slater Type Orbitals
+ Advantages: Have a complete set
Radial behavior closely matches hydrogenic
orbitals
Disadvantages:
No nodes, as with H-like orbitals
Not mutually orthogonal
For larger molecules, computer evaluation of the
many integrals involved is quite time consuming
Need to reduce the computational cost
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CCCE 2008
Possible Basis Functions
3. Gaussian Type Orbitals (GTOs)
Proposed by S.F. Boys in 1950
GTO form:
0.5
2( 2 n + 1.5)
( 2 n + 1)/ 4 ( n 1) ( r 2 ) m
g( r , , ) =
r
e
Yl ( , )
( 2n 1)!
+ Advantages: Have a complete set
Computer evaluation of integrals much faster
Closed integrals; Integrated GTO gives a GTO
Disadvantages: Not mutually orthogonal
Representation of e- probability is poor near and
far away from the nucleus
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CCCE 2008
Comparison
STO vs. GTO
1.2
1
0.8
0.6
0.4
0.2
0
STO: e-r
GTO: e-r2
STO
GTO
0.5
1.5
2.5
3.5
4.5
Radius
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GTOs
Linear combinations of GTOs are used to
approximate STOs (which are themselves
approximations)
A single GTO basis function has significant errors
when compared to a STO, especially near the
nucleus (See previous slide)
If several GTOs are combined in a linear
combination, the basis function is greatly
improved
See next slide
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Comparisons
STO vs. GTOs
0.9
0.8
Wavefunction
0.7
0.6
STO
0.5
GTO
0.4
STO-3G
0.3
0.2
0.1
0
0
Radius (Angstroms)
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Use of GTOs
Individual GTOs not used as basis functions:
Use a normalized linear combination of a few
GTOs (called primitives), each with different
values to give a contracted Gaussian function
gc =
c g
i
where gc is a contracted gaussian,
g p is a primitive gaussian, and ci is
a contraction coefficient
A linear combination of these primitives (typically
1-7) is used to approximate the STO
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Use of GTOs
Using contracted GTOs instead of primitive
GTOs as the basis set has advantages:
Number of variational coefficients to be
determined is reduced, which saves a lot of
computational time
Accuracy is NOT reduced significantly, as long as
the contraction coefficients (cis) are well chosen
Increasing the number of primitive GTOs used in
each contracted Gaussian improves the accuracy
Different types of basis sets use different numbers
and types of GTOs
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Minimal Basis Sets
Jargon Used STO-NG (Single )
N is the number of primitive GTOs used
Example: STO-3G
Three primitive GTOs used per AO
Popular starting point for calculations
STO-3G basis functions have been developed for
most of the elements in the Periodic table
Minimal basis sets do not adequately describe
non-spherical (anisotropic) electron distribution in
molecules (as in polar covalent bonds)
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Minimal Basis Sets
GTO representation of a STO for 1s AO:
s
1STO
( r ) = 0.5 1.5e( r )
3
where = 1
3
2
2
2
2 4
2 4
2 4
1sSTO-3G ( r ) = c1 1 e( 1r ) + c2 2 e( 2r ) + c3 3 e( 3r )
where c1 = 0.444615, c2 = 0.535336, c3 = 0154340
.
and 1 = 0109818
.
, 2 = 0.405771, 3 = 0.2.22766
c values are called the contraction coefficients
The exponents are the alpha () values
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Split Valence Basis Sets
Jargon Used K-LMG (Double )
Differentiate between core and valence electrons
Developed to overcome problems of inadequate
description of anisotropic electron distributions
using minimal basis sets (Size is adjusted)
K = number of sp-type inner shell primitive GTOs
L = number of inner valence s- and p-type primitive
GTOs
M = number of outer valence s- and p-type
primitive GTOs
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Split Valence Basis Sets
Each split valence atomic orbital is composed of a
variable proportion of two (or more) functions of
different size or radial extent
For a larger e- cloud
(longer bond)
a<b
For a smaller e- cloud
(shorter bond)
a>b
a and b are normalized and sum to 1
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Split Valence Basis Sets
Examples:
3-21G (Used as the semiempirical basis set)
Three primitives for the inner shell (STO-3G); each
valence orbital is constructed with two sizes of
basis function (Two GTOs for contracted valence
orbitals; One GTO for extended valence orbitals)
6-311G
STO-6G for inner shell; Three sizes of basis
function for each valence orbital (Three GTOs for
contracted valence orbitals, and two different sizes
of GTO for extended valence orbitals)
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Polarized Basis Sets
Jargon Used 6-31G(d) or 6-31G* (older)
Also have 6-31G(d,p) or 6-31G**
(d) or * type
d-type functions added to atoms with Z > 2
f-type functions added to transition metals
(d,p) or ** type
p-type functions added to H atoms
d-type functions added to atoms with Z > 2
f-type functions added to transition metals
6-31G(d) is another popular basis set choice
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Polarized Basis Sets
In molecule formation, AOs become distorted
in shape (polarization)
Orbitals are influenced by other nuclei
Polarization accounts for these influences which
distort the orbital shape
+
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Diffuse Basis Sets
Jargon Used 6-31+G(d) or 6-31++G(d)
6-31+G(d)
6-31G(d) basis set with an additional larger pfunction for atoms with Z > 2
6-31++G(d)
6-31+G(d) basis set with an additional larger sfunction for H atoms
Diffuse basis sets are useful for describing
anions, molecules with lone pairs, excited
states, and transition states (loosely held e-)
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Basis Set Progression
Increasing number of GTOs Used:
Minimal < Split Valence < Polarized < Diffuse
Get an increasingly good approximation to the actual
wave function
The number of integrals increases as N4 where N
is the number of basis functions
During the minimization process, the orbital
exponents are adjusted to define a new basis set to
start another iteration
Computational cost has to be considered
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CCCE 2008
Comparison of Some Methods for Accuracy
HF
B
A
S
I
S
S
E
T
Minimal
STO-3G
Split Valence
3-21G
Polarized
6-31G(d) ~ DZVP
6-311G(d,p) ~ TZVP
DFT Location??
MP2
MP3
MP4 QCISD(T) ...
Full CI
Electron Correlation
Diffuse
6-311+G(d,p)
High ang.
Momentum
6-311+G(2d,p)
6-311++G(3df,3dp)
........
Schrdinger
Equation
HF
Limit
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CCCE 2008
Basis Set Choice and Expense
axial-methylcyclohexane on SGI Indigo2
(Spartan cpu time in sec.)
Method/Basis Set
AM1/STO-3G
HF/STO-3G
HF/ 3-21G(d)
HF/ 6-31G(d,p)
s.p.
~1
72
193
2632
opt.
10
983
2214
34655 (9.6 h)
As larger basis sets are used, the energy decreases
(Variational Principle)
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Common Basis Sets
Brief Description of Standard Basis Sets
Basis Set
Description
STO-3G
Minimal basis; qualitative results - large systems
3-21G
Double ; more accurate results on large systems
6-31G(d)
Moderate set; Common use for medium systems
6-31G(d,p)
Used where H is site of interest; More accurate
6-31+G(d)
Used with anions, excited states, lone pairs, etc.
6-31+G(d,p) Used with anions, etc., where H is site of interest
6-311++G(d,p) Good for final, accurate energies, but expensive
Many other sets are in use. Existing sets can be modified
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Optimization of a Basis Set
Variational Principle: Energy values are
bounded from below
The lower the calculated energy, the better
Procedure:
Vary the constants and exponents that describe the
Gaussian functions sequentially until the lowest
energy is obtained
Such a basis set may only apply to that
individual molecule, however
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Lab: Gaussian Orbitals
Question: How are Gaussian orbitals used to
approximate a Slater Type Orbital?
Importance: Basis sets are approximations
based on mathematical use of two or more
Gaussian functions
Goal: Visualize an STO-3G basis set what does the resultant function look like?
Computational Tool: Spreadsheet
Refer to Basis Set Case Study handout for
detailed instructions
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