期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 103, 期 39, 页码 14282-14287出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0603679103
关键词
ab initio molecular dynamics; hydrated electron; photoelectron spectroscopy
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.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据