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Implementation and Validation of Constrained Density Functional Theory Forces in the CP2K Package

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [1]
  1. University College London (United Kingdom)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
+ Show Author Affiliations

Constrained density functional theory (CDFT) is a powerful tool for the prediction of electron transfer parameters in condensed phase simulations at a reasonable computational cost. In this work we present an extension to CDFT in the popular mixed Gaussian/plane wave electronic structure package CP2K, implementing the additional force terms arising from a constraint based on Hirshfeld charge partitioning. This improves upon the existing Becke partitioning scheme, which is prone to give unphysical atomic charges. We verify this implementation for a variety of systems: electron transfer in (H2O)2+ in vacuum, electron tunnelling between oxygen vacancy centers in solid MgO, and electron self-exchange in aqueous Ru2+-Ru3+. We find good agreement with previous plane-wave CDFT results for the same systems, but at a significantly lower computational cost, and we discuss the general reliability of condensed phase CDFT calculations.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Engineering and Physical Sciences Research Council (EPSRC)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1886909
Report Number(s):
PNNL-SA-173919
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 7 Vol. 18; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY