Chapter: 5 Basis sets
Different traditions:
Quantum chemistry (HF,DFT) Solid state physics(DFT)
Local Slater/Gaussian orbitals Plane waves
Nowadays: Gaussian, Slater, Plane waves, GAPW
Numerical grids, wavelets.......
Chapter: 5 Local basis sets
φi = ΣΑ,υ cAiυχΑυ χΑυ is a basis function centered on atom A
χΑυ(rA) = R(rA)Ylm(ϑA,θA) s-orbital: Ylm: 1
p-orbital: Ylm: x/r, y/r, z/r
d-orbital: Ylm: (3z2-r2)/r2, xy/r2, (x2-y2)/r2, xz/r2,yz/r2
…..................
Slater type orbitals: R = Nrne-αr (STO)
Gaussian type orbitals: R = Nrne-αr2 (GTO)
Contracted Gaussian Type Orbitals, CGTO:
χCGTOµ = Σ aλµχGTOλ (χGTOλ primitive function, one value of α)
aλµ : contraction coefficient, fixed from atoms
Number/complexity of integrals Number of coefficients
The size of a basis set:
The number of contracted basis functions
Minimal basis = single ζ (zeta):
One (contracted) function per atomic orbital (1s, 2s, 2p (px, py, px)..)
Double ζ (DZ): two (contracted) functions per atomic orbital, e.g.
DZV = double ζ valence = single ζ for core orbitals and double ζ
(DZ) for valence orbitals
Polarization functions: functions corresponding to atomic orbitals
with higher l-quantum numbers, not occupied in the atom
e.g. C atom (DZV + polarization):
3s (1s=1, 2s=2), 2p (2p=2(*3)), 1d (pol=1(*5))
Diffuse functions: functions with low exponents
Example: H2O DZV(D95)
1 2 3 4 5
(A1)--O (A1)--O (B2)--O (A1)--O (B1)--O
EIGENVALUES -20.55978 -1.34010 -0.70839 -0.54700 -0.49737
1 1 O 1S 0.99579 -0.21355 0.00000 -0.07136 0.00000
2 2S 0.02188 0.47092 0.00000 0.17167 0.00000
3 2PX 0.00000 0.00000 0.00000 0.00000 0.64105
4 2PY 0.00000 0.00000 0.50045 0.00000 0.00000
5 2PZ -0.00200 -0.10103 0.00000 0.55578 0.00000
6 3S -0.00789 0.48887 0.00000 0.28771 0.00000
7 3PX 0.00000 0.00000 0.00000 0.00000 0.51062
8 3PY 0.00000 0.00000 0.27187 0.00000 0.00000
9 3PZ 0.00181 -0.05845 0.00000 0.41584 0.00000
10 2 H 1S 0.00011 0.13441 0.26017 -0.13784 0.00000
11 2S 0.00192 -0.00705 0.12204 -0.08290 0.00000
12 3 H 1S 0.00011 0.13441 -0.26017 -0.13784 0.00000
13 2S 0.00192 -0.00705 -0.12204 -0.08290 0.00000
Plus 9 virtual orbitals:
Example: H2O TZV-P 1 2 3 4 5
(A1)--O (A1)--O (B2)--O (A1)--O (B1)--O
EIGENVALUES -20.54488 -1.32720 -0.70579 -0.55701 -0.49598
1 1 O 1S 0.55146 -0.11403 0.00000 -0.03589 0.00000
2 2S 0.47169 -0.19059 0.00000 -0.06098 0.00000
3 2PX 0.00000 0.00000 0.00000 0.00000 0.29219
4 2PY 0.00000 0.00000 0.22350 0.00000 0.00000
5 2PZ -0.00176 -0.03239 0.00000 0.25653 0.00000
6 3S 0.00545 0.54375 0.00000 0.18544 0.00000
7 3PX 0.00000 0.00000 0.00000 0.00000 0.43663
8 3PY 0.00000 0.00000 0.34419 0.00000 0.00000
9 3PZ 0.00065 -0.05562 0.00000 0.38092 0.00000
10 4S -0.00043 0.38627 0.00000 0.30513 0.00000
11 4PX 0.00000 0.00000 0.00000 0.00000 0.46890
12 4PY 0.00000 0.00000 0.21300 0.00000 0.00000
13 4PZ -0.00010 -0.01992 0.00000 0.35853 0.00000
14 5D 0 -0.00002 0.00151 0.00000 -0.01600 0.00000
15 5D+1 0.00000 0.00000 0.00000 0.00000 -0.01623
16 5D-1 0.00000 0.00000 -0.02729 0.00000 0.00000
17 5D+2 0.00015 -0.00782 0.00000 0.00557 0.00000
18 5D-2 0.00000 0.00000 0.00000 0.00000 0.00000
19 2H 1S 0.00019 0.08956 0.14802 -0.08480 0.00000
20 2S 0.00011 0.07918 0.21366 -0.13843 0.00000
21 3S 0.00009 -0.00194 0.05703 -0.03363 0.00000
22 4PX 0.00000 0.00000 0.00000 0.00000 0.02964
23 4PY -0.00009 -0.02391 -0.02171 0.02722 0.00000
24 4PZ 0.00002 0.01351 0.02481 0.01005 0.00000
25 3H 1S 0.00019 0.08956 -0.14802 -0.08480 0.00000
26 2S 0.00011 0.07918 -0.21366 -0.13843 0.00000
Plus 25 virtual orbitals 27 3S 0.00009 -0.00194 -0.05703 -0.03363 0.00000
28 4PX 0.00000 0.00000 0.00000 0.00000 0.02964
29 4PY 0.00009 0.02391 -0.02171 -0.02722 0.00000
30 4PZ 0.00002 0.01351 -0.02481 0.01005 0.00000
Nomenclature of basis sets in the Gaussian program:
k-nlmG
G: Gaussian type functions
k: # of primitive core functions
# of nl… : # of contracted valence functions
n: # of primitive functions in 1st contraction
l: # of primitive functions in 2nd contraction
m: # of primitive functions in 3rd contraction
e.g. 3-21G = DZV
6-311G = TZV
6-311++G(2d,2p)
First + : diffuse functions on ”heavy atoms”
Second + : diffuse functions on H
2d: 2 polarization functions on ”heavy atoms”
2p: 2 polarization functions on H
Effective core potentials (ECP)
Inner shell electrons are described by a fixed potential (compare O1s in H2O)
Advantages:
1. Less electrons to treat
2. Less basis functions needed
3. Relativistic effects can be implicitly included (intermediately heavy atoms)
Disadvantages:
• Relies on frozen core approximation (can therefore be less accurate)
Example:
Pd atom:1s22s22p63s23p63d10 | 4s24p64d10
All electron: 46 electrons, 45 basis functions
ECP: 18 electrons, 27 basis functions (e.g. lanl2 in Gaussian)
About basis sets and accuracy
Basis set superposition errors (BSSE): An atom is ”using” the basis
set of another atom => too large binding energies. No BSSE with
Counterpoise correction sometimes important. plane waves !
Hartree-Fock limit: For some systems rather large basis sets are
needed to converge the Hartree-Fock energy.
Complete
Basis set
Correlation energy: Very large basis sets needed to converge the
Limit
correlation energy (MP2, CI, CCSD etc).
Gaussians
DFT: Less sensitive to the basis set. Plane waves
(Semi-)Local approx. for exchange-correlation functional. Grids
Geometry optimization: Can be done with rather small basis sets
(double zeta). Single point calculations with larger basis sets give
good relative energies.
