OH stretching frequencies in systems with intramolecular hydrogen bonds

Harmonic and anharmonic analyses

Jens Spanget-Larsen, Bjarke Knud Vilster Hansen, Poul Erik Hansen

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

OH stretching wavenumbers were investigated for 30 species with intramolecularly hydrogen-bonded hydroxyl groups, covering the range from 3600 to ca. 1900 cm−1. Theoretical wavenumbers were predicted with B3LYP/6-31G(d) density functional theory using the standard harmonic approximation, as well as the second-order perturbation theoretical (PT2) anharmonic approximations available with the Gaussian software package. The wavenumbers computed with the anharmonic procedures were found to be essentially linearly related to those obtained within the harmonic analysis. The theoretical wavenumbers were compared with experimental values taken from the literature, supplemented with values estimated from infrared (IR) absorption spectra recorded for the purpose of this study. An approximately linear relationship was established between the observed wavenumbers νOH and the results of the harmonic analysis. This is significant in view of the fact that the full anharmonic PT2 analysis requires orders-of-magnitude more computing time than the harmonic analysis. νOH also correlates with OH chemical shifts.
OriginalsprogEngelsk
TidsskriftChemical Physics
Vol/bind389
Udgave nummer1-3
Sider (fra-til)107-115
Antal sider9
ISSN0301-0104
DOI
StatusUdgivet - 2011

Citer dette

@article{f9285247db87492891f87589985cc355,
title = "OH stretching frequencies in systems with intramolecular hydrogen bonds: Harmonic and anharmonic analyses",
abstract = "OH stretching wavenumbers were investigated for 30 species with intramolecularly hydrogen bonded hydroxyl groups, covering the range from 3600 to ca. 1900 cm-1. Theoretical wavenumbers were predicted with B3LYP/6-31G(d) density functional theory using the standard harmonic approximation, as well as the second-order perturbation theoretical (PT2) anharmonic approximations available with the GAUSSIAN software package. The wavenumbers computed with the anharmonic procedures were found to be essentially linearly related to those obtained within the harmonic analysis. The theoretical wavenumbers were compared with experimental values taken from the literature, supplemented with values estimated from infrared (IR) absorption spectra recorded for the purpose of this study. An approximately linear relationship was established between the observed wavenumbers νOH and the results of the harmonic analysis. This is significant in view of the fact that the full anharmonic PT2 analysis requires orders-of-magnitude more computing time than the harmonic analysis. νOH also correlates with OH chemical shifts.",
keywords = "DFT calculations, harmonic, anharmonic, vibrational spectra, intramolecular hydrogen bonding",
author = "Jens Spanget-Larsen and Hansen, {Bjarke Knud Vilster} and Hansen, {Poul Erik}",
year = "2011",
doi = "10.1016/j.chemphys.2011.09.011",
language = "English",
volume = "389",
pages = "107--115",
journal = "Chemical Physics",
issn = "0301-0104",
publisher = "Elsevier BV",
number = "1-3",

}

OH stretching frequencies in systems with intramolecular hydrogen bonds : Harmonic and anharmonic analyses. / Spanget-Larsen, Jens; Hansen, Bjarke Knud Vilster; Hansen, Poul Erik.

I: Chemical Physics, Bind 389, Nr. 1-3, 2011, s. 107-115.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - OH stretching frequencies in systems with intramolecular hydrogen bonds

T2 - Harmonic and anharmonic analyses

AU - Spanget-Larsen, Jens

AU - Hansen, Bjarke Knud Vilster

AU - Hansen, Poul Erik

PY - 2011

Y1 - 2011

N2 - OH stretching wavenumbers were investigated for 30 species with intramolecularly hydrogen bonded hydroxyl groups, covering the range from 3600 to ca. 1900 cm-1. Theoretical wavenumbers were predicted with B3LYP/6-31G(d) density functional theory using the standard harmonic approximation, as well as the second-order perturbation theoretical (PT2) anharmonic approximations available with the GAUSSIAN software package. The wavenumbers computed with the anharmonic procedures were found to be essentially linearly related to those obtained within the harmonic analysis. The theoretical wavenumbers were compared with experimental values taken from the literature, supplemented with values estimated from infrared (IR) absorption spectra recorded for the purpose of this study. An approximately linear relationship was established between the observed wavenumbers νOH and the results of the harmonic analysis. This is significant in view of the fact that the full anharmonic PT2 analysis requires orders-of-magnitude more computing time than the harmonic analysis. νOH also correlates with OH chemical shifts.

AB - OH stretching wavenumbers were investigated for 30 species with intramolecularly hydrogen bonded hydroxyl groups, covering the range from 3600 to ca. 1900 cm-1. Theoretical wavenumbers were predicted with B3LYP/6-31G(d) density functional theory using the standard harmonic approximation, as well as the second-order perturbation theoretical (PT2) anharmonic approximations available with the GAUSSIAN software package. The wavenumbers computed with the anharmonic procedures were found to be essentially linearly related to those obtained within the harmonic analysis. The theoretical wavenumbers were compared with experimental values taken from the literature, supplemented with values estimated from infrared (IR) absorption spectra recorded for the purpose of this study. An approximately linear relationship was established between the observed wavenumbers νOH and the results of the harmonic analysis. This is significant in view of the fact that the full anharmonic PT2 analysis requires orders-of-magnitude more computing time than the harmonic analysis. νOH also correlates with OH chemical shifts.

KW - DFT calculations

KW - harmonic

KW - anharmonic

KW - vibrational spectra

KW - intramolecular hydrogen bonding

U2 - 10.1016/j.chemphys.2011.09.011

DO - 10.1016/j.chemphys.2011.09.011

M3 - Journal article

VL - 389

SP - 107

EP - 115

JO - Chemical Physics

JF - Chemical Physics

SN - 0301-0104

IS - 1-3

ER -