Modelling Electron Transfers Using Quasidiabatic Hartree-Fock States

Abstract

Electron transfer processes are ubiquitous in chemistry and of great importance in many systems of biological and commercial interest. The ab-initio description of these processes remains a challenge in theoretical chemistry, partly due to the high scaling of many post-Hartree--Fock computational methods. This poses a problem for systems of interest that are not easily investigated experimentally. We show that readily available Hartree--Fock solutions can be used as a quasidiabatic basis to understand electron transfer reactions in a Marcus framework. Non-orthogonal configuration interaction calculations can be used to quantify interactions between the resulting electronic states, and to investigate the adiabatic electron transfer process. When applied to a titanium-alizarin complex used as a model of a Grätzel-type solar cell, this approach yields a correct description of the electron transfer and provides information about the electronic states involved in the process.

References in corpus (3)

• Semiclassical Green's functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit
• Holomorphic Hartree-Fock Theory: The Nature of Two-Electron Problems
• Holomorphic Hartree-Fock Theory and Configuration Interaction

Cited by in corpus (9)

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• Complex Adiabatic Connection: a Hidden Non-Hermitian Path from Ground to Excited States
• Generalized nonorthogonal matrix elements for arbitrary excitations
• Holomorphic Density Functional Theory
• Selected non-orthogonal configuration interaction with compressed single and double excitations
• Localized and delocalized states of a diamine cation: A critical test of wave function methods
• On Symmetry and the Reality of Holomorphic Hartree--Fock Wavefunctions