Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 103, Issue 39, Pages 14282-14287Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0603679103
Keywords
ab initio molecular dynamics; hydrated electron; photoelectron spectroscopy
Categories
Ask authors/readers for more resources
Despite numerous experiments and static electronic structure calculations, the nature of hydrated-electron clusters, (H2O)(n)(-), remains poorly understood. Here, we introduce a hybrid ab initio molecular dynamics scheme, balancing accuracy against feasibility, to simulate vibrational and photoelectron spectra of (H2O)(n)(-), treating all electrons quantum-mechanically. This methodology provides a computational tool for understanding the spectra of weakly bound and supramolecular anions and for elucidating the fingerprint of dynamics in these spectra. Simulations of (H2O)(4)(-) provide quantitative agreement with experimental spectra and furnish direct evidence of the nonequilibrium nature of the cluster ensemble that is probed experimentally. The simulations also provide an estimate of the cluster temperature (T approximate to 150-200 K) that is not available from experiment alone. The double acceptor electron-binding motif is found to be highly stable with respect to thermal fluctuations, even at T = 300 K, whereas the extra electron stabilizes what would otherwise be unfavorable water configurations.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available