ISSN:
1432-2234
Keywords:
Intermolecular interactions
;
Perturbation theory
;
Second quantization
;
Biorthogonal basis
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00186447
