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Calculation of transition matrix elements by nonsingular orbital transformations
Author(s) -
Kývala Mojmír
Publication year - 2009
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.21935
Subject(s) - wave function , invertible matrix , atomic orbital , transformation (genetics) , molecular orbital , slater type orbital , slater determinant , matrix (chemical analysis) , basis (linear algebra) , chemistry , computational chemistry , delocalized electron , simple (philosophy) , function (biology) , transformation matrix , basis function , physics , quantum mechanics , molecular orbital theory , molecule , mathematics , geometry , biochemistry , philosophy , chromatography , epistemology , evolutionary biology , kinematics , biology , gene , electron
A general strategy is described for the evaluation of transition matrix elements between pairs of full class CI wave functions built up from mutually nonorthogonal molecular orbitals. A new method is proposed for the counter‐transformation of the linear expansion coefficients of a full CI wave function under a nonsingular transformation of the molecular‐orbital basis. The method, which consists in a straightforward application of the Cauchy–Binet formula to the definition of a Slater determinant, is shown to be simple and suitable for efficient implementation on current high‐performance computers. The new method appears mainly beneficial to the calculation of miscellaneous transition matrix elements among individually optimized CASSCF states and to the re‐evaluation of the CASCI expansion coefficients in Slater‐determinant bases formed from arbitrarily rotated (e.g., localized or, conversely, delocalized) active molecular orbitals. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009