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Electronic coupling matrix elements from charge constrained density functional theory calculations using a plane wave

Harald Oberhofer¹, Jochen Blumberger

¹Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.

The Journal of Chemical Physics

|January 5, 2011

Summary

This summary is machine-generated.

We developed a new computational method using constrained density functional theory (CDFT) to calculate electronic coupling for electron transfer reactions. This approach accurately models thermal effects, revealing significant fluctuations in electron transfer rates.

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Area of Science:

Computational Chemistry
Quantum Chemistry
Electron Transfer Theory

Background:

Calculating electronic coupling matrix elements is crucial for understanding electron transfer reactions.
Constrained Density Functional Theory (CDFT) offers a framework for these calculations.
Previous methods often relied on local basis sets or approximations.

Purpose of the Study:

To implement a plane wave basis set for calculating electronic coupling matrix elements within CDFT.
To investigate the impact of thermal fluctuations on electron transfer.
To provide a method applicable to extended systems with quantum mechanical treatment of donor, acceptor, and environment.

Main Methods:

Developed a plane wave basis set implementation for CDFT.
Approximated diabatic wavefunctions using Kohn-Sham determinants from CDFT.
Employed an efficient integration scheme for coupling matrix element calculation.
Utilized density functional based molecular dynamics to sample thermal fluctuations.

Main Results:

The plane wave CDFT method shows excellent agreement with high-level ab initio calculations for intermolecular electron transfer.
Thermal fluctuations, particularly molecular bending, can alter electron transfer rates by over an order of magnitude.
Generalized gradient approximation (GGA) functionals are suitable for intermolecular transfer, but exact exchange is necessary for intramolecular systems like Q-TTF-Q(-) to match experimental data.

Conclusions:

The plane wave basis set implementation for CDFT is a robust method for calculating electronic coupling matrix elements.
Thermal fluctuations significantly influence electron transfer dynamics, with the thermal average coupling being substantially higher than the minimum energy structure value.
The choice of functional (GGA vs. exact exchange) is critical for accurate results, depending on the specific electron transfer system.