Perturbative calculation of intermolecular interactions in orthogonalized or biorthogonal basis sets |
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| Authors: | P R Surján C Pérez del Valley |
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| Institution: | (1) Present address: Dept. Theoretical Chemistry, Eötvös University, POB 32, H-1518 Budapest 112, Hungary;(2) Instituto de Matematicas y Fisica Fundamental, Serrano 123, 28006 Madrid, Spain |
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| Abstract: | Two versions of a many-body perturbation theory for the computation of molecular interaction energies are investigated. The methods are based on the partitioning of the second-quantized form of the dimer Hamiltonian written either in the orthogonalized basis of the monomer MOs, or, alternatively, in the original non-orthogonal dimer basis set handling the overlap by the biorthogonal formalism. The zeroth-order Hamiltonian H
0 is the sum of effective monomer Fockians and the zeroth-order wave functions are exact eigenfunctions of H
0. Full antisymmetry is ensured by the second-quantized formalism. Basis set superposition error is accounted for by the counterpoise correction recipe. Results for He2, (H2)2 and (H2O)2 indicate the reliability of the biorthogonal technique. |
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| Keywords: | Intermolecular interactions Perturbation theory Second quantization Biorthogonal basis |
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