Excited State Nonadiabatic Molecular Dynamics of Hot Electron Addition to Water Clusters in the Ultrafast Femtosecond Regime

Leighton O. Jones; George C. Schatz

doi:10.1021/acs.jpclett.3c00386

Excited State Nonadiabatic Molecular Dynamics of Hot Electron Addition to Water Clusters in the Ultrafast Femtosecond Regime

Leighton O. Jones, George C. Schatz^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

Dissociative electron attachment (DEA) reactions of water result in the production of hydrogen atoms and hydroxide anions. This has been studied for a long time and is relatively slow in liquid water for thermalized hydrated electrons but much faster with a higher-energy electron. Here, we probe the nonadiabatic molecular dynamics after the addition of a hot electron (6-7 eV) to a neutral water cluster (H₂O)_n, where n = 2-12, considering the 0-100 fs time scale using the fewest switches surface hopping method, in conjunction with ab initio molecular dynamics and the Tamm-Dancoff approximation density functional theory method. The nonadiabatic DEA occurs within 10-60 fs, and with high probability, giving H + OH^- above an energy threshold. This is faster than time scales estimated previously for autoionization or adiabatic DEA. The change in threshold energy with cluster size is modest, ranging from 6.6 to 6.9 eV. Dissociation on a femtosecond time scale is consistent with pulsed radiolysis experiments.

Original language	English (US)
Pages (from-to)	3521-3526
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	14
Issue number	14
DOIs	https://doi.org/10.1021/acs.jpclett.3c00386
State	Published - Apr 13 2023

Funding

The authors thank Peter Bruggeman for valuable comments. This research was sponsored by the Army Research Office and was accomplished under Grant W911NF-20-1-0105. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of the Army Research Office or the U.S. Government. The U.S. Government is authorized to reproduce and distribute reprints for Government purposes notwithstanding any copyright notation herein. The theory research was supported in part through the computational resources and staff contributions provided for the Quest high-performance computing facility at Northwestern University, which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology.

ASJC Scopus subject areas

General Materials Science
Physical and Theoretical Chemistry

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10.1021/acs.jpclett.3c00386

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title = "Excited State Nonadiabatic Molecular Dynamics of Hot Electron Addition to Water Clusters in the Ultrafast Femtosecond Regime",

abstract = "Dissociative electron attachment (DEA) reactions of water result in the production of hydrogen atoms and hydroxide anions. This has been studied for a long time and is relatively slow in liquid water for thermalized hydrated electrons but much faster with a higher-energy electron. Here, we probe the nonadiabatic molecular dynamics after the addition of a hot electron (6-7 eV) to a neutral water cluster (H2O)n, where n = 2-12, considering the 0-100 fs time scale using the fewest switches surface hopping method, in conjunction with ab initio molecular dynamics and the Tamm-Dancoff approximation density functional theory method. The nonadiabatic DEA occurs within 10-60 fs, and with high probability, giving H + OH- above an energy threshold. This is faster than time scales estimated previously for autoionization or adiabatic DEA. The change in threshold energy with cluster size is modest, ranging from 6.6 to 6.9 eV. Dissociation on a femtosecond time scale is consistent with pulsed radiolysis experiments.",

author = "Jones, {Leighton O.} and Schatz, {George C.}",

note = "Funding Information: The authors thank Peter Bruggeman for valuable comments. This research was sponsored by the Army Research Office and was accomplished under Grant W911NF-20-1-0105. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of the Army Research Office or the U.S. Government. The U.S. Government is authorized to reproduce and distribute reprints for Government purposes notwithstanding any copyright notation herein. The theory research was supported in part through the computational resources and staff contributions provided for the Quest high-performance computing facility at Northwestern University, which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

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N2 - Dissociative electron attachment (DEA) reactions of water result in the production of hydrogen atoms and hydroxide anions. This has been studied for a long time and is relatively slow in liquid water for thermalized hydrated electrons but much faster with a higher-energy electron. Here, we probe the nonadiabatic molecular dynamics after the addition of a hot electron (6-7 eV) to a neutral water cluster (H2O)n, where n = 2-12, considering the 0-100 fs time scale using the fewest switches surface hopping method, in conjunction with ab initio molecular dynamics and the Tamm-Dancoff approximation density functional theory method. The nonadiabatic DEA occurs within 10-60 fs, and with high probability, giving H + OH- above an energy threshold. This is faster than time scales estimated previously for autoionization or adiabatic DEA. The change in threshold energy with cluster size is modest, ranging from 6.6 to 6.9 eV. Dissociation on a femtosecond time scale is consistent with pulsed radiolysis experiments.

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Excited State Nonadiabatic Molecular Dynamics of Hot Electron Addition to Water Clusters in the Ultrafast Femtosecond Regime

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