Density Functional Theory
Density Functional Theory
Lecture 8
Gaussian basis sets
C.-K. Skylaris
AOs on atom A
AOs on atom B
AOs on atom C
Example: find the AOs from which the MOs of the following molecules will
be built
Basis functions
We can take the LCAO concept one step further:
Use a larger number of AOs (e.g. a hydrogen atom can have more than one s AO,
and some p and d AOs, etc.). This will achieve a more flexible representation of
our MOs and therefore more accurate calculated properties according to the
variation principle
Use AOs of a particular mathematical form that simplifies the computations (but
are not necessarily equal to the exact AOs of the isolated atoms)
coefficient
(a number, to be
determined by the
SCF calculation)
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However, Gaussian functions are preferred in practice because they allow for efficient
computation of molecular integrals (simpler formulas)
Slater function
Gaussian function
l=k+m+n
s functions
d functions
p functions
etc.
s functions
d functions
p functions
etc.
STO-2G
The simplest kind of CGs are the
STO-nG basis sets
These basis sets attempt to
approximate Slater-type orbitals
(STOs) by n primitive Gaussians
STO-3G
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One CG per core atomic orbital and more than one for the valence atomic
orbitals, e.g.: SV, 3-21G, 4-31G, 6-31G, 6-311G
Write down how many CGs some of the above basis sets will include for the
following atoms: H, C, S
And for the following molecules: H2O, CH4
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Basis set
STO-3G
STO-6G
6-31G
6-31++G
6-31G**
6-31++G**
H2O energy
H3O+ energy Protonation
Protonation
(Eh)
(Eh)
energy (Eh) energy (kcal/mol)
-75.3133
-75.6817
-0.3684
-231.2
-76.0366
-76.4015
-0.3649
-229.0
-76.3852
-76.6721
-0.2869
-180.1
-76.4000
-76.6753
-0.2753
-172.7
-76.4197
-76.7056
-0.2859
-179.4
-76.4341
-76.7078
-0.2738
-171.8
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aug-cc-pvqz
aug-cc-pvqz_diffuse
aug-cc-pvt+dz
aug-cc-pvt+dz_diffuse
aug-cc-pvtz
aug-cc-pvtz_diffuse
bauschlicher_ano
binning-curtiss_1d_polarization
binning-curtiss_df_polarization
binning_curtiss_sv
binning_curtiss_svp
binning_curtiss_vtz
binning_curtiss_vtzp
blaudeau_polarization
cc-pcv5z
cc-pcv6z
cc-pcvdz
cc-pcvqz
cc-pcvtz
cc-pv5+dz
cc-pv5z
cc-pv5z_dk
cc-pv5zfi_sf_fw
cc-pv5zfi_sf_lc
cc-pv5zfi_sf_sc
cc-pv5zpt_sf_fw
cc-pv5zpt_sf_lc
cc-pv5zpt_sf_sc
cc-pv6+dz
cc-pv6z
cc-pvd+dz
cc-pvdz
cc-pvdz_dk
cc-pvdzfi_sf_fw
cc-pvdzfi_sf_lc
cc-pvdzfi_sf_sc
cc-pvdz-fit2-1
cc-pvdzpt_sf_fw
cc-pvdzpt_sf_lc
cc-pvdzpt_sf_sc
cc-pvdzseg-opt
cc-pvq+dz
cc-pvqz
cc-pvqz_dk
cc-pvqzfi_sf_fw
cc-pvqzfi_sf_lc
cc-pvqzfi_sf_sc
cc-pvqzpt_sf_fw
cc-pvqzpt_sf_lc
cc-pvqzpt_sf_sc
cc-pvqzseg-opt
cc-pvt+dz
cc-pvtz
cc-pvtz_dk
cc-pvtzfi_sf_fw
cc-pvtzfi_sf_lc
cc-pvtzfi_sf_sc
cc-pvtz-fit2-1
cc-pvtzpt_sf_fw
cc-pvtzpt_sf_lc
cc-pvtzpt_sf_sc
cc-pvtzseg-opt
chipman_dzp_+_diffuse
core_val._functions_cc-pcv5z
core_val._functions_cc-pcv6z
core_val._functions_cc-pcvdz
core_val._functions_cc-pcvqz
core_val._functions_cc-pcvtz
crenbl_ecp
crenbs_ecp
d-aug-cc-pv5z
d-aug-cc-pv5z_diffuse
d-aug-cc-pv6z
d-aug-cc-pv6z_diffuse
d-aug-cc-pvdz
d-aug-cc-pvdz_diffuse
d-aug-cc-pvqz
d-aug-cc-pvqz_diffuse
d-aug-cc-pvtz
d-aug-cc-pvtz_diffuse
demon_coulomb_fitting
dgauss_a1_dft_coulomb_fitting
dgauss_a1_dft_exchange_fitting
dgauss_a2_dft_coulomb_fitting
dgauss_a2_dft_exchange_fitting
dhms_polarization
dunning-hay_diffuse
dunning-hay_double_rydberg
dunning-hay_rydberg
dz_+_double_rydberg_dunning-hay
dz_dunning
dzp_+_diffuse_dunning
dzp_dunning
dzp_+_rydberg_dunning
dz_+_rydberg_dunning
dzvp2_dft_orbital
dzvp_dft_orbital
feller_misc._cvdz
feller_misc._cvqz
feller_misc._cvtz
gamess_pvtz
gamess_vtz
glendening_polarization
hay-wadt_mb_n+1_ecp
hay-wadt_vdz_n+1_ecp
hondo7_polarization
huzinaga_polarization
lanl2dzdp_ecp
lanl2dzdp_ecp_polarization
lanl2dz_ecp
mclean_chandler_vtz
midi!
midi_huzinaga
mini_huzinaga
mini_scaled
nasa_ames_ano
nasa_ames_cc-pcv5z
nasa_ames_cc-pcvqz
nasa_ames_cc-pcvtz
nasa_ames_cc-pv5z
nasa_ames_cc-pvqz
nasa_ames_cc-pvtz
partridge_uncontr._1
partridge_uncontr._2
partridge_uncontr._3
pople_2d_2p_polarization
pople_2df_2pd_polarization
pople_3df_3pd_polarization
pople-style_diffuse
pv6z
qmmm_zhang_3-21g_ecp
qmmm_zhang_6-31gs_ecp
sadlej_pvtz
sbkjc_vdz_ecp
sdb-aug-cc-pvqz
sdb-aug-cc-pvqz_diffuse
sdb-aug-cc-pvtz
sdb-aug-cc-pvtz_diffuse
sdb-cc-pvqz
sdb-cc-pvtz
sto-2g
sto-3g
sto-3gs
sto-3gs_polarization
sto-6g
stuttgart_rlc_ecp
stuttgart_rsc_1997_ecp
stuttgart_rsc_ano_ecp
stuttgart_rsc_segmented_ecp
sv_+_double_rydberg_dunning-hay
sv_dunning-hay
svp_+_diffuse_dunning-hay
svp_+_diffuse_+_rydberg
svp_dunning-hay
svp_+_rydberg_dunning-hay
sv_+_rydberg_dunning-hay
tz_dunning
tzvp_dft_orbital
wachters+f
wtbs
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contraction
coefficients
exponents
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Homework
1) Describe how many and what type (s, p, d) primitive and contracted Gaussians you will have in the STO-2G, DZP
and 3-21G basis sets for the O atom.
2) The 3-21G* basis set for a carbon atom can be input into a quantum chemistry program using the following
parameters (exponents and contraction coefficients):
C
S
172.256000000
25.910900000
5.533350000
SP
3.664980000
0.770545000
SP
0.195857000
0.06176690
0.35879400
0.70071300
-0.39589700
1.21584000
0.23646000
0.86061900
1.00000000
1.00000000
Which of the above parameters describe functions for the core electrons, valence electrons and for polarisation?
Describe how you can uncontract the basis set and what effect this would have on your calculations.
3) Substitute the expression for the basis set expansion of a molecular orbital into the Schrdinger equation for the
Kohn-Sham orbitals and derive a matrix representation of the Schrdinger equation, involving the matrix
elements of the Kohn-Sham Hamiltonian
and the overlap matrix of the basis functions
(which are not orthogonal). This matrix equation can be solved on a computer to obtain the orbital expansion
coefficients (diagonalisation of the Hamiltonian matrix) and is part of the traditional SCF procedure.
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5-minute quiz
Name :
Surname:
Date :
1) Why are Slater functions more suitable than Gaussians as basis functions?
2) What do we mean when we say that a basis set contains polarisation functions and what do we mean by
diffuse functions?
3) What is a double-zeta basis set? Would you expect a triple-zeta basis set to give better results than STO-3G
and why?
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