Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions

Tamal Mukherjee, Naoki Ito, Ian Gould

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.

Original languageEnglish (US)
Pages (from-to)1837-1843
Number of pages7
JournalJournal of Physical Chemistry A
Volume115
Issue number10
DOIs
StatePublished - Mar 17 2011

Fingerprint

Charge transfer
electron transfer
charge transfer
Electrons
optical control
Optical links
Dipole moment
polarization (charge separation)
Rate constants
polarity
emission spectra
dipole moments
absorption spectra
energy
Hot Temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions. / Mukherjee, Tamal; Ito, Naoki; Gould, Ian.

In: Journal of Physical Chemistry A, Vol. 115, No. 10, 17.03.2011, p. 1837-1843.

Research output: Contribution to journalArticle

@article{32bee8e0e94a4f4c85388a1c3cbafffd,
title = "Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions",
abstract = "The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.",
author = "Tamal Mukherjee and Naoki Ito and Ian Gould",
year = "2011",
month = "3",
day = "17",
doi = "10.1021/jp108625y",
language = "English (US)",
volume = "115",
pages = "1837--1843",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions

AU - Mukherjee, Tamal

AU - Ito, Naoki

AU - Gould, Ian

PY - 2011/3/17

Y1 - 2011/3/17

N2 - The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.

AB - The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.

UR - http://www.scopus.com/inward/record.url?scp=79952577243&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79952577243&partnerID=8YFLogxK

U2 - 10.1021/jp108625y

DO - 10.1021/jp108625y

M3 - Article

C2 - 21341820

AN - SCOPUS:79952577243

VL - 115

SP - 1837

EP - 1843

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 10

ER -