Model for the effects of a condensed phase on the infrared spectra of hydrogen-bonded systems

Notker Rösch, Mark A Ratner

Research output: Contribution to journalArticle

120 Citations (Scopus)

Abstract

A formal scheme is developed for treating the effects of a condensed phase on the vibrational spectrum of hydrogen-bonded systems. A coupling of the moving proton to the bath is assumed responsible for the broadening, and is taken as simply the electrostatic interaction between the protonic dipole and the random local field set up by the internal modes of the bath or solvent. This corresponds to the electrostatic broadening. A strong-coupling treatment is employed. The spectrum is found by a cumulant expansion of the dipole-dipole correlation function. Expressions for the shift and broadening of the individual lines are given. The dynamics, as well as the strength, of the system-bath coupling are important for determining lineshape. The lineshape is thus related to the microscopic dynamic behavior of the hydrogen-bonded system in solution.

Original languageEnglish
Pages (from-to)3344-3351
Number of pages8
JournalJournal of Chemical Physics
Volume61
Issue number8
Publication statusPublished - 1974

Fingerprint

Hydrogen
baths
infrared spectra
dipoles
Infrared radiation
Vibrational spectra
hydrogen
Coulomb interactions
electrostatics
Protons
Electrostatics
vibrational spectra
expansion
protons
shift
interactions

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Model for the effects of a condensed phase on the infrared spectra of hydrogen-bonded systems. / Rösch, Notker; Ratner, Mark A.

In: Journal of Chemical Physics, Vol. 61, No. 8, 1974, p. 3344-3351.

Research output: Contribution to journalArticle

@article{a397d852e21e4c17928f556fecae62cf,
title = "Model for the effects of a condensed phase on the infrared spectra of hydrogen-bonded systems",
abstract = "A formal scheme is developed for treating the effects of a condensed phase on the vibrational spectrum of hydrogen-bonded systems. A coupling of the moving proton to the bath is assumed responsible for the broadening, and is taken as simply the electrostatic interaction between the protonic dipole and the random local field set up by the internal modes of the bath or solvent. This corresponds to the electrostatic broadening. A strong-coupling treatment is employed. The spectrum is found by a cumulant expansion of the dipole-dipole correlation function. Expressions for the shift and broadening of the individual lines are given. The dynamics, as well as the strength, of the system-bath coupling are important for determining lineshape. The lineshape is thus related to the microscopic dynamic behavior of the hydrogen-bonded system in solution.",
author = "Notker R{\"o}sch and Ratner, {Mark A}",
year = "1974",
language = "English",
volume = "61",
pages = "3344--3351",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "8",

}

TY - JOUR

T1 - Model for the effects of a condensed phase on the infrared spectra of hydrogen-bonded systems

AU - Rösch, Notker

AU - Ratner, Mark A

PY - 1974

Y1 - 1974

N2 - A formal scheme is developed for treating the effects of a condensed phase on the vibrational spectrum of hydrogen-bonded systems. A coupling of the moving proton to the bath is assumed responsible for the broadening, and is taken as simply the electrostatic interaction between the protonic dipole and the random local field set up by the internal modes of the bath or solvent. This corresponds to the electrostatic broadening. A strong-coupling treatment is employed. The spectrum is found by a cumulant expansion of the dipole-dipole correlation function. Expressions for the shift and broadening of the individual lines are given. The dynamics, as well as the strength, of the system-bath coupling are important for determining lineshape. The lineshape is thus related to the microscopic dynamic behavior of the hydrogen-bonded system in solution.

AB - A formal scheme is developed for treating the effects of a condensed phase on the vibrational spectrum of hydrogen-bonded systems. A coupling of the moving proton to the bath is assumed responsible for the broadening, and is taken as simply the electrostatic interaction between the protonic dipole and the random local field set up by the internal modes of the bath or solvent. This corresponds to the electrostatic broadening. A strong-coupling treatment is employed. The spectrum is found by a cumulant expansion of the dipole-dipole correlation function. Expressions for the shift and broadening of the individual lines are given. The dynamics, as well as the strength, of the system-bath coupling are important for determining lineshape. The lineshape is thus related to the microscopic dynamic behavior of the hydrogen-bonded system in solution.

UR - http://www.scopus.com/inward/record.url?scp=0001503141&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001503141&partnerID=8YFLogxK

M3 - Article

VL - 61

SP - 3344

EP - 3351

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 8

ER -