Jack Simons , Henry Eyring Scientist and Professor Chemistry Department University of Utah

1. Electronic Structure Theory Session 6 Jack Simons, Henry Eyring Scientist and Professor Chemistry Department University of Utah

2. Now that the use of AO bases for determining HF MOs has been discussed, let’s return to discuss how one includes electron correlation in a calculation using a many determinant wave function  = L CL1,L2,...LN |L1L2L...LN| There are many ways for finding the CL1,L2,...LN coefficients, and each has certain advantages and disadvantages. Møller-Plesset perturbation (MPPT): one uses a single-determinant SCF process to determine a set of orthonormal spin-orbitals {i}. Then, using H0equal to the sum of the N electrons’ Fock operators H0 = i=1,N F(i), perturbation theory is used to determine the CIamplitudes for the CSFs. The amplitude for the reference determinantis taken as unity and the other determinants' amplitudes are determined by Rayleigh-Schrödinger perturbation using H-H0 as the perturbation.

3. The first (and higher) order corrections to the wave function are then expanded in terms of Slater determinants 1 = L1,L2,L2,…LN CL1,L2,…LN |L1L2L3 … LN | and Rayleigh-Schrödinger perturbation theory (H0 -E0) 1 = (E1 -V) 0 is used to solve for E1 =  0* V 0 d=  0* (H-H0) 0 d= -1/2k,l=occ. [< k(1) l(2)|e2/r1,2| k(1) l(2)> - < k(1) l(2)|e2/r1,2| l(1) k(2)>] and for 1 = i<j(occ) m<n(virt) [< ij | e2/r1,2 | mn > -< ij | e2/r1,2 | nm >] [ m-i +n-j]-1|i,jm,n > wherei,jm,nis a Slater determinant formed by replacingi bym andjbyn in the zeroth-order Slater determinant.

4. There are no singly excited determinantsim in 1because • im*(H-H0) 0 d= 0 according to Brillouin’s theorem (if HF spin-orbitals are used to form0and to define H0). So,E1just corrects E0 for the double-counting error that summing the occupied orbital energies gives. 1 contains no singly excited Slater determinants, but has only doubly excited determinants. Recall that doubly excited determinants can be thought of as allowing for dynamical correlation as polarized orbital pairs are formed.

5. The second order energy correction from RSPT is obtained from (H0-E0) 2 = (E1-V)1 + E20. Multiplying this on the left by0* and integrating over all of the N electrons’s coordinates gives E2 =  0* V 1 d. Using the earlier result for 1 gives: E2 i<j(occ) m<n(virt)[< ij | e2/r1,2 | mn > -< ij | e2/r1,2 | nm >]2 [ m-i +n-j]-1 Thus at the MP2 level, the correlation energy is a sum of spin-orbital pair correlation energies. Higher order corrections (MP3, MP4, etc.) are obtained by using the RSPT approach. Note that large correlation energies should be expected whenever one has small occupied-virtual orbital energy gaps for occ. and virt. orbitals that occupy the same space.

6. MPn has strengths and weaknesses. Disadvantages: Should not use if more than one determinant is important because it assumes the reference determinant is dominant. The MPn energies often do not converge

7. The lack of convergence can give rise to “crazy” potential curves. The MPn energies are size extensive. No choices of “important” determinants beyond0needed secent scaling at low order (M5 for MP2).