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An efficient method for calculating static polarizabilities from a correlated wave function
Author(s) -
Chacon Monique Revorêdo,
Zerner Michael C.
Publication year - 1994
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560490506
Subject(s) - configuration interaction , dipole , hamiltonian (control theory) , wave function , full configuration interaction , chemistry , function (biology) , physics , quantum mechanics , mathematics , excited state , mathematical optimization , evolutionary biology , biology
We present a method closely related to configuration interaction over single excitations ( CI‐S ) for the calculation of static dipole moments and polarizabilities, which we call modified configuration interaction over single excitations ( MCI‐S ). This method allows for orbital relaxation through the inclusion of single excitations on a correlated first‐order Rayleigh–Schrödinger wave function. An approximation to our MCI‐S results in an inexpensive method to calculate polarizabilities that yields good results when compared with the full configuration interaction ( CI‐F ) results. This method, called modified configuration interaction over single excitations without triple excitations ( MCI‐S_WT ), seems particularly suitable to applications for large systems. Examples are presented using the intermediate neglect of the differential overlap model Hamiltonian ( INDO/1 ), which indicates that the MCI‐S_WT procedure presents an error of less than 15% with respect to the CI‐F values in a fraction of the computational effort. © 1994 John Wiley & Sons, Inc.