Electron-transfer reactions in water. Contributions from high-frequency librations?

Joseph T Hupp, Thomas J. Meyer

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

From the solvent dependence of the absorption band energies for metal-to-metal charge-transfer bands in several symmetrical ligand-bridged mixed-valence dimers, water emerges as an anomalous solvent. Explanations based on specific ligand-solvent interactions or the involvement of high-frequency hydroxyl stretching modes are shown to be inconsistent with the available results. The experimental observations can be accomodated, however, by postulating the involvement of relatively high-frequency librational modes known to exist in water. The observation of anomalously high MMCT band energies in water has significant implications for related electron-transfer reactions such as thermally activated self-exchanges.

Original languageEnglish
Pages (from-to)1001-1003
Number of pages3
JournalJournal of Physical Chemistry
Volume91
Issue number5
Publication statusPublished - 1987

Fingerprint

libration
electron transfer
Electrons
Water
Metals
Ligands
water
ligands
Hydroxyl Radical
Dimers
Band structure
metals
Stretching
energy bands
Charge transfer
Absorption spectra
dimers
charge transfer
valence
absorption spectra

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Electron-transfer reactions in water. Contributions from high-frequency librations? / Hupp, Joseph T; Meyer, Thomas J.

In: Journal of Physical Chemistry, Vol. 91, No. 5, 1987, p. 1001-1003.

Research output: Contribution to journalArticle

@article{9d129f86c593474a90208ec95afad52c,
title = "Electron-transfer reactions in water. Contributions from high-frequency librations?",
abstract = "From the solvent dependence of the absorption band energies for metal-to-metal charge-transfer bands in several symmetrical ligand-bridged mixed-valence dimers, water emerges as an anomalous solvent. Explanations based on specific ligand-solvent interactions or the involvement of high-frequency hydroxyl stretching modes are shown to be inconsistent with the available results. The experimental observations can be accomodated, however, by postulating the involvement of relatively high-frequency librational modes known to exist in water. The observation of anomalously high MMCT band energies in water has significant implications for related electron-transfer reactions such as thermally activated self-exchanges.",
author = "Hupp, {Joseph T} and Meyer, {Thomas J.}",
year = "1987",
language = "English",
volume = "91",
pages = "1001--1003",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Electron-transfer reactions in water. Contributions from high-frequency librations?

AU - Hupp, Joseph T

AU - Meyer, Thomas J.

PY - 1987

Y1 - 1987

N2 - From the solvent dependence of the absorption band energies for metal-to-metal charge-transfer bands in several symmetrical ligand-bridged mixed-valence dimers, water emerges as an anomalous solvent. Explanations based on specific ligand-solvent interactions or the involvement of high-frequency hydroxyl stretching modes are shown to be inconsistent with the available results. The experimental observations can be accomodated, however, by postulating the involvement of relatively high-frequency librational modes known to exist in water. The observation of anomalously high MMCT band energies in water has significant implications for related electron-transfer reactions such as thermally activated self-exchanges.

AB - From the solvent dependence of the absorption band energies for metal-to-metal charge-transfer bands in several symmetrical ligand-bridged mixed-valence dimers, water emerges as an anomalous solvent. Explanations based on specific ligand-solvent interactions or the involvement of high-frequency hydroxyl stretching modes are shown to be inconsistent with the available results. The experimental observations can be accomodated, however, by postulating the involvement of relatively high-frequency librational modes known to exist in water. The observation of anomalously high MMCT band energies in water has significant implications for related electron-transfer reactions such as thermally activated self-exchanges.

UR - http://www.scopus.com/inward/record.url?scp=0001429501&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001429501&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001429501

VL - 91

SP - 1001

EP - 1003

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 5

ER -