Hydrated electron dynamics: From cluster to bulk

A. E. Bragg; J. R.R. Verlet; A. Kammrath; O. Cheshnovsky; D. M. Neumark

doi:10.1126/science.1103527

Hydrated electron dynamics: From cluster to bulk

A. E. Bragg, J. R.R. Verlet, A. Kammrath, O. Cheshnovsky, D. M. Neumark^*

^*Corresponding author for this work

School of Chemistry

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

248 Scopus citations

Abstract

The electronic relaxation dynamics of size-selected (H₂O) _n^-/(D₂O)_n^- [25 ≤ n ≤ 50] clusters have been studied with time-resolved photoelectron imaging. The excess electron (e_c^-) was excited through the e _c^-(p) ← e_c^-(s) transition with an ultrafast laser pulse, with subsequent evolution of the excited state monitored with photodetachment and photoelectron imaging. All clusters exhibited p-state population decay with concomitant s-state repopulation (internal conversion) on time scales ranging from 180 to 130 femtoseconds for (H ₂O)_n^- and 400 to 225 femtoseconds for (D ₂O)_n^-; the lifetimes decrease with increasing cluster sizes. Our results support the "nonadiabatic relaxation" mechanism for the bulk hydrated electron (e_aq^-), which invokes a 50-femtosecond e_aq^-(p) → e _aq^-(s^t) internal conversion lifetime.

Original language	English
Pages (from-to)	669-671
Number of pages	3
Journal	Science
Volume	306
Issue number	5696
DOIs	https://doi.org/10.1126/science.1103527
State	Published - 22 Oct 2004

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title = "Hydrated electron dynamics: From cluster to bulk",

abstract = "The electronic relaxation dynamics of size-selected (H2O) n-/(D2O)n- [25 ≤ n ≤ 50] clusters have been studied with time-resolved photoelectron imaging. The excess electron (ec-) was excited through the e c-(p) ← ec-(s) transition with an ultrafast laser pulse, with subsequent evolution of the excited state monitored with photodetachment and photoelectron imaging. All clusters exhibited p-state population decay with concomitant s-state repopulation (internal conversion) on time scales ranging from 180 to 130 femtoseconds for (H 2O)n- and 400 to 225 femtoseconds for (D 2O)n-; the lifetimes decrease with increasing cluster sizes. Our results support the {"}nonadiabatic relaxation{"} mechanism for the bulk hydrated electron (eaq-), which invokes a 50-femtosecond eaq-(p) → e aq-(st) internal conversion lifetime.",

author = "Bragg, {A. E.} and Verlet, {J. R.R.} and A. Kammrath and O. Cheshnovsky and Neumark, {D. M.}",

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T1 - Hydrated electron dynamics

T2 - From cluster to bulk

AU - Bragg, A. E.

AU - Verlet, J. R.R.

AU - Kammrath, A.

AU - Cheshnovsky, O.

AU - Neumark, D. M.

PY - 2004/10/22

Y1 - 2004/10/22

N2 - The electronic relaxation dynamics of size-selected (H2O) n-/(D2O)n- [25 ≤ n ≤ 50] clusters have been studied with time-resolved photoelectron imaging. The excess electron (ec-) was excited through the e c-(p) ← ec-(s) transition with an ultrafast laser pulse, with subsequent evolution of the excited state monitored with photodetachment and photoelectron imaging. All clusters exhibited p-state population decay with concomitant s-state repopulation (internal conversion) on time scales ranging from 180 to 130 femtoseconds for (H 2O)n- and 400 to 225 femtoseconds for (D 2O)n-; the lifetimes decrease with increasing cluster sizes. Our results support the "nonadiabatic relaxation" mechanism for the bulk hydrated electron (eaq-), which invokes a 50-femtosecond eaq-(p) → e aq-(st) internal conversion lifetime.

AB - The electronic relaxation dynamics of size-selected (H2O) n-/(D2O)n- [25 ≤ n ≤ 50] clusters have been studied with time-resolved photoelectron imaging. The excess electron (ec-) was excited through the e c-(p) ← ec-(s) transition with an ultrafast laser pulse, with subsequent evolution of the excited state monitored with photodetachment and photoelectron imaging. All clusters exhibited p-state population decay with concomitant s-state repopulation (internal conversion) on time scales ranging from 180 to 130 femtoseconds for (H 2O)n- and 400 to 225 femtoseconds for (D 2O)n-; the lifetimes decrease with increasing cluster sizes. Our results support the "nonadiabatic relaxation" mechanism for the bulk hydrated electron (eaq-), which invokes a 50-femtosecond eaq-(p) → e aq-(st) internal conversion lifetime.

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Hydrated electron dynamics: From cluster to bulk

Abstract

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