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Proton-transfer dynamics in ionized water chains using real-time time-dependent density functional theory

Vidushi Sharma and Marivi Fernández-Serra
Phys. Rev. Research 2, 043082 – Published 15 October 2020
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Abstract

In density functional–theoretic studies of photoionized water-based systems, the role of charge localization in proton-transfer dynamics is not well understood. This is due to the inherent complexity in extracting the contributions of coupled electron-nuclear nonadiabatic dynamics in the presence of exchange and correlation functional errors. In this work we address this problem by simulating a model system of ionized linear H-bonded water clusters using real-time time-dependent density functional theory–based Ehrenfest dynamics. Our aim is to understand how self-interaction error in semilocal exchange and correlation functionals affects the probability of proton transfer. In particular, we show that the proton-transfer probability is largely underestimated for short H-bonded chains but becomes comparable to that predicted by hybrid functionals for (H2O)n+ chains with n>3. This is because the formation of hemibonded-type geometries is largely suppressed in extended H-bonded structures. We also show how the degree of localization of the initial photo-hole is connected to the probability of a proton-transfer reaction, as well as to the hole–proton separation. These results are compared to those obtained with adiabatic dynamics where the initial wave function is allowed to relax to the ground state of the ion cluster, explaining why different functionals and dynamical approaches lead to quantitatively different results.

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  • Received 23 July 2020
  • Revised 8 September 2020
  • Accepted 15 September 2020

DOI:https://doi.org/10.1103/PhysRevResearch.2.043082

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

Published by the American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied Physics

Authors & Affiliations

Vidushi Sharma* and Marivi Fernández-Serra

  • Department of Physics and Astronomy, Stony Brook University, Stony Brook, New York 11794-3800, USA and Institute for Advanced Computational Science, Stony Brook University, Stony Brook, New York 11794-5250, USA

  • *vidushi.sharma@stonybrook.edu
  • maria.fernandez-serra@stonybrook.edu

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Issue

Vol. 2, Iss. 4 — October - December 2020

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