Computational Material Science Part II. Ito Chao ( ) Institute of Chemistry Academia Sinica

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1 Computational Material Science Part II Ito Chao ( ) Institute of Chemistry Academia Sinica

2 Ab Initio Implementations of Hartree-Fock Molecular Orbital Theory Fundamental assumption of HF theory: each electron sees all of the others as an average field (lack of electron correlation) ab initio (Latin for from the beginning ) HF: solve the HF equations with no additional approximations. Use equivalent of an infinite basis set to reach HF limit (E HF ). E correlation = E true -E HF E HF E true E correlation

3 Basis set Ψ = Slater determinant formed from the individual occupied MO; each MO is expressed as a linear combination of basis functions For the general case (use χ to express both the spatial and spin parts of the equation) PREREQUISITE: wave function should have large amplitude in regions of space where the electron probability density is large use atomic orbital?

4 - Slater-type orbitals (STO) and Gaussian-type orbitals (GTO) Gaussian-type Slater-type Slater-type orbital (e -r ) has no analytical solution for four index integral Boys proposed Gaussian-type AO-like orbitals i + j + k = 0 => s i = 1 => p x ; j = 1 => p y ; k = 1 => p z i + j + k = 2 => d Cartesian d functions: x 2, y 2, z 2, xy, xz, yz Canonical d functions: xy, xz, yz, x 2 -y 2, 3z 2 r 2

5 Problems of GTO: Gaussian-type Slater-type 1) No cusp at atomic center, 2) Too rapid a reduction in amplitude with distance 3) No radial nodal behavior Solution: linear combination of GTOs to reproduce STOs number of gaussian functions exponent decides shape Basis function Gaussian function chosen to optimize shape and ensure normalization

6 STO-MG (Slater-Type Orbital approximated by M Gaussians) primitive gaussian In a contracted basis function, c a are fixed. Slater Contracted Gaussian STO-3G more often used than other STO-MG Notation for contraction: (6s3p/3s)/[2s1p/1s] H atom 1st row atom

7 Single-ζ, Multiple-ζ, and Split-Valence basis sets - STO-3G is single-ζ : only one basis function for each AO Exponent for s and p are the same to save computing time (called sp basis function). Advantage: (ss ss) = (ss sp) = (ss pp) = (sp sp) for the radial part. Negative sign to get nodal characteristics Disadvantage of STO-3G: not flexible enough to represent electron population in molecules

8 - Multiple-ζ : decontract to increase flexibility of wavefunction Ex: double-ζ : 2 functions for each AO triple-ζ: 3 functions for each AO Compare STO-3G and double-ζ with three gaussian functions STO-3G: 3 primitive Gaussian contracted as 1 function double-ζ: 2 functions--the first function being a contraction of 2 primitive the second function being normalized third primitive => size of secular equation larger for double-ζ

9 - Split-valence (valence multiple-ζ) : decontract to increase flexibility of the valence electrons (core electrons are less involved in bonding, still use contracted functions) Ex: 6-31G (by Pople) 6 primitive Gaussian functions for contracted core function 3 primitive Gaussian functions for contracted valence function 1 primitive for uncontracted valence function 1G Valence orbital 2p: 32G For O atom: 1s 2s 2p x 2p y 2p z STO-3G = G = G = 13

10 Polarization Functions and Diffusion Functions Inversion barrier of pyramidal NH kcal/mol N HF calc. with atomic centered basis set of s and p functions predicts planar geometry! Not enough mathematical flexibility for molecules. => adding basis functions not centered on atomic center (floating gaussian orbitals FLOGO) -less used => adding basis functions corresponding to one quantum number of higher angular momentum than the valence orbitals (polarization functions) First row atom C, N, O, : add d orbitals H: add p orbitals Pyramidal geometry obtained from HF calc. Although some error in energy due to lack of electron correlation

11 Ex: d orbital for better bonding of O Ex: d orbitals needed to describe hypervalent bonding situations in phophates, sulfoxides O O S O P

12 Highest energy MOs of anion, highly excited states, loose supermolecular complexes => Spatially diffuse! OH => adding basis functions that are more diffuse (diffuse functions) Ex: additional one s and one set of p functions having small exponents Stnadard valence size larger size as diffuse function

13 - Pople s nomenclature Ex: 6-31+G* or 6-31+G(d) polarization functions on nonhydrogen (heavy) atom diffuse function on nonhydrogen (heavy) atom Ex: G** or 6-31+G(d,p) polarization functions on hydrogen atom second + means diffuse function on hydrogen atom Ex: G(3df,2pd) Ex: 3-21G(*) 2 sets of p functions and 1 set of d function 3 sets of d functions, 1 set of f functions on heavy atom * in parenthesis means no d functions for 1st row atoms (C, N, O )

14 - Other conventions MIDI (by Huzinaga) MIDI! Or MIDIX (polarization functions on non-carbon heavy atoms) MIDIY (polarization functions on hydrogen atom as well) MIDIX+ cc-pvnz (correlation-consistent polarized valence zeta; by Dunning) n: D (double zeta), T (triple zeta), Q (quadruple zeta) D: d on heavy atoms; p on H atom T: 1 set of f and 2 sets of d on heavy; 1 set of d and 2 sets of p on H Ex: aug-cc-pv6z (very expensive!) 1 i, 2 h, 3g, 4 f, 5 d, 6 p and s, in addition to core functions aug (augmented) means diffuse functions used The general impression you should get: Pople s basis set => popular; MIDI => not expensive; cc-pvnz => expensive

15 The HF Limit Too large to calculate! Not practical for most case.

16 - The additive assumption # of basis function Less than half the time of evalution at the HF/ G(d,p) level!

17 Effective Core Potential (ECP) Replace the core electrons with analytical functions to represent the combined nuclear-electronic core to the remaining electrons - reduce the # of electrons in calculation - fold in the relativistic effects of heavy elements - small-core (scale back to the next lower shell) and largecore (exclude only the outermost shell) approaches both present in the literature Commonly used ones: By Hay and Wadt; LANL ECPs (Los Alamos National Laboratory) non-relativistic for the first row of transition metals Check optimized polarization and diffuse functions for LANL double-zeta basis set for p block elements By Stevens By Dolg; Stuttgart-Dresden ECPs More recent ones: By Lavallo and Klobukowski; for 1st row transition metals By Dyall; for 4p, 5p, and 6p elements; correlation-consistent

18 A good electronic source of basis sets

19 RHF, ROHF, UHF Wavefunctions - RHF (spin-restricted), ROHF (restricted open-shell HF) α and β spins occupy the same spatial orbital ROHF ROHF thoery produces wave functions that are eigenfunctions of the spin operator S 2, but fails to account for spin polarization

20 - UHF (spin-unrestricted) α and β spins occupy different spatial orbitals UHF UHF does not produces wave functions that are eigenfunctions of the spin operator S 2, but can account for spin polarization Spin contamination: UHF wave function incorporates some degree of contamination from higher spin states Doublets contaminated by quartets, extets, octets Triplets contaminated by pentets, heptets, nonets Degree of contamination can be judged from <S 2 > Eigenvalue Eigenvalueof of the the spin spin operator operator <S <S 2 2 > = S(S+1) S(S+1) S = vector vector sum sum of of spin spin magnetic magnetic moment moment for for doublet; doublet; for for triplet; triplet; for for quartet quartet If <S 2 > larger than expected value by 5%, do not use Problem of spin contamination!

21 General strategies for efficient calculations - Use symmetry Reduce the dimension of degree of freedom and the size of matrix. Caution: may introduced undesirable contraints - Use wave function, geometry, Hessian matrix from lower level results => easier to converge, time saving! => important for large molecules or high level calculations

22 Performance of ab initio HF Theory - Reaction energy: not very good (because electrons are in different bonding situations, less error canceling) - Conformer energy difference: ok Larger basis set may not guarantee better results because basis set imcompleteness and failure to account for electron correlation may introduce errors of opposite sign -The secret of success of Koopman s theory (E HOMO = -IP) (orbital relaxation and the electron correlation effects offset one another) orbital relaxation A + electron correlation A