Møller-Plesset correlation energies in a localized orbital basis using a Laplace transform technique

SummaryIn electronic structure calculations requiring the handling of large amounts of integrals, storage requirements can often be reduced through the use of localized orbitals which gives rise to sparse integral arrays. However, conventional Møller-Plesset perturbation theory is constrained to canonical orbitals due to the explicit use of orbital energies in the energy expressions, and it is therefore not straightforward to reduce the storage requirements through such orbital localization. This work shows how the constraint of canonical orbitals can be lifted using a Laplace transform technique, and investigates the reduction in storage requirement that can result from the localization of orbitals made possible by such an approach.

[1]  J. Pople,et al.  Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals , 1969 .

[2]  Stephen Wolfram,et al.  Mathematica: a system for doing mathematics by computer (2nd ed.) , 1991 .

[3]  Jan Almlöf,et al.  Elimination of energy denominators in Møller—Plesset perturbation theory by a Laplace transform approach , 1991 .

[4]  J. Almlöf,et al.  Principles for a direct SCF approach to LICAO–MOab‐initio calculations , 1982 .

[5]  P Pulay,et al.  Local Treatment of Electron Correlation , 1993 .

[6]  Jan Almlöf,et al.  Laplace transform techniques in Mo/ller–Plesset perturbation theory , 1992 .

[7]  Paul G. Mezey,et al.  A fast intrinsic localization procedure applicable for ab initio and semiempirical linear combination of atomic orbital wave functions , 1989 .

[8]  S. F. Boys.  Construction of Some Molecular Orbitals to Be Approximately Invariant for Changes from One Molecule to Another , 1960 .

[9]  G. Scuseria.  Ab initio theoretical predictions of the equilibrium geometries of C60, C60H60 and C60F60 , 1991 .

[10]  Clifford E. Dykstra,et al.  Advanced theories and computational approaches to the electronic structure of molecules , 1984 .

[11]  Michael J. Frisch,et al.  MP2 energy evaluation by direct methods , 1988 .

[12]  Klaus Ruedenberg,et al.  Localized Atomic and Molecular Orbitals , 1963 .

[13]  Peter Pulay,et al.  Orbital-invariant formulation and second-order gradient evaluation in Møller-Plesset perturbation theory , 1986 .

[14]  Marco Häser,et al.  Improvements on the direct SCF method , 1989 .

[15]  T. H. Dunning.  Gaussian Basis Functions for Use in Molecular Calculations. III. Contraction of (10s6p) Atomic Basis Sets for the First‐Row Atoms , 1970 .

[16]  Svein Saebo,et al.  Avoiding the integral storage bottleneck in LCAO calculations of electron correlation , 1989 .