Efficient Constrained Density Functional Theory Implementation for Simulation of Condensed Phase Electron Transfer Reactions

Nico Holmberg; Kari Laasonen

doi:10.1021/acs.jctc.6b01085

Efficient Constrained Density Functional Theory Implementation for Simulation of Condensed Phase Electron Transfer Reactions

J Chem Theory Comput. 2017 Feb 14;13(2):587-601. doi: 10.1021/acs.jctc.6b01085. Epub 2017 Jan 9.

Authors

Nico Holmberg¹, Kari Laasonen¹

Affiliation

¹ COMP Centre of Excellence in Computational Nanoscience, Department of Chemistry, Aalto University , P.O. Box 16100, FI-00076 Aalto, Finland.

PMID: 28009515
DOI: 10.1021/acs.jctc.6b01085

Abstract

Constrained density functional theory (CDFT) is a versatile tool for probing the kinetics of electron transfer (ET) reactions. In this work, we present a well-scaling parallel CDFT implementation relying on a mixed basis set of Gaussian functions and plane waves, which has been specifically tailored to investigate condensed phase ET reactions using an explicit, quantum chemical representation of the solvent. The accuracy of our implementation is validated against previous theoretical results for predicting electronic couplings and charge transfer energies. Subsequently, we demonstrate the efficiency of our method by studying the intramolecular ET reaction of an organic mixed-valence compound in water using a CDFT based molecular dynamics simulation.