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Probability current in protein electron transfer: Löwdin population analysis
Author(s) -
de Andrade Paulo Cesar Peres
Publication year - 2012
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.24197
Subject(s) - linear subspace , population , electron , chemistry , electron density , electron transfer , current (fluid) , basis (linear algebra) , atomic physics , operator (biology) , physics , molecular physics , quantum mechanics , mathematics , thermodynamics , geometry , biochemistry , demography , repressor , sociology , gene , transcription factor
We consider the problem of building an electron probability current density in subspaces of the full Hilbert space in case where there are overlaps between the subspaces and its complements. In this case, the projectors onto these subspaces are non‐Hermitian and one has different possible electron population analysis. We show how the electron probability current density can be directly constructed from the probability conservation equation and relate them to population operators. For the Löwdin population operator, we investigated the electron probability current density in protein electron transfer problem when the medium are described with nonorthogonal atomic basis set, and contrast it with Mulliken analysis. Analytical comparison among interatomic currents shows that others interatomic currents can be obtained as a combination of these interatomic currents provided by the nonorthogonal analysis. The overlapping atomic population analysis is obtained with nonorthogonal projectors and provides interatomic currents different of the previous results. In case of strong coupling between protein and donor/acceptor, the normalized interatomic current used recently to build a vectorial pathway model can depend on the surface in the protein medium between the donor and acceptor sites. © 2012 Wiley Periodicals, Inc.