TY - JOUR
T1 - Excited State Nonadiabatic Molecular Dynamics of Hot Electron Addition to Water Clusters in the Ultrafast Femtosecond Regime
AU - Jones, Leighton O.
AU - Schatz, George C.
N1 - 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:
© 2023 American Chemical Society.
PY - 2023/4/13
Y1 - 2023/4/13
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.
AB - 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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U2 - 10.1021/acs.jpclett.3c00386
DO - 10.1021/acs.jpclett.3c00386
M3 - Article
C2 - 37014704
AN - SCOPUS:85152206150
SN - 1948-7185
VL - 14
SP - 3521
EP - 3526
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 14
ER -