{ital Ab initio} quantum chemical calculation of electron transfer matrix elements for large molecules

Journal Article · Tue Jul 01 04:00:00 EDT 1997 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.474406· OSTI ID:530063

Zhang, L Y; Friesner, R A ^[1]; Murphy, R B ^[2]

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1. Department of Chemistry, Columbia University, New York, New York 10027 (United States)
2. Schroedinger, Inc., Portland, Oregon 97204 (United States)

Using a diabatic state formalism and pseudospectral numerical methods, we have developed an efficient {ital ab initio} quantum chemical approach to the calculation of electron transfer matrix elements for large molecules. The theory is developed at the Hartree{endash}Fock level and validated by comparison with results in the literature for small systems. As an example of the power of the method, we calculate the electronic coupling between two bacteriochlorophyll molecules in various intermolecular geometries. Only a single self-consistent field (SCF) calculation on each of the monomers is needed to generate coupling matrix elements for all of the molecular pairs. The largest calculations performed, utilizing 1778 basis functions, required {approximately}14h on an IBM 390 workstation. This is considerably less cpu time than would be necessitated with a supermolecule adiabatic state calculation and a conventional electronic structure code. {copyright} {ital 1997 American Institute of Physics.}

• DOE Contract Number: FG02-90ER14162
• OSTI ID: 530063
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 107; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
BIOLOGICAL MATERIALS
CHARGE EXCHANGE
CHLOROPHYLL
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
MATRIX ELEMENTS
MOLECULES
QUANTUM MECHANICS
SELF-CONSISTENT FIELD