Electronic Excited State Lifetimes of Anionic Water Clusters: Dependence on Charge Solvation Motif

Daniel Borgis, Peter J. Rossky, L. Túri

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

An ongoing controversy about water cluster anions concerns the electron-binding motif, whether the charge center is localized at the surface or within the cluster interior. Here, mixed quantum-classical dynamics simulations have been carried out for a wide range of cluster sizes (n ≤ 1000) for (H2O)n- and (D2O)n-, based on a nonequilibrium first-order rate constant approach. The computed data are in good general agreement with time-resolved photoelectron imaging results (n ≤ 200). The analysis reveals that, for surface state electrons, the cluster size dependence of the excited state electronic energy gap and the magnitude of the nonadiabatic couplings have compensating influences on the excited state lifetimes: the excited state lifetime for surface states reaches a minimum for n ∼ 150 and then increases for larger clusters. It is concluded that the electron resides in a surface-localized motif in all of these measured clusters, dominating at least up to n = 200.

Original languageEnglish
Pages (from-to)2304-2309
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume8
Issue number10
DOIs
Publication statusPublished - May 18 2017

ASJC Scopus subject areas

  • Materials Science(all)

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