Far-infrared VRT spectroscopy of the water dimer: Characterization of the 20 μ m out-of-plane librational vibration

William T.S. Cole; Ray S. Fellers; Mark R. Viant; Claude Leforestier; Richard J. Saykally

doi:10.1063/1.4933116

Far-infrared VRT spectroscopy of the water dimer: Characterization of the 20 μ m out-of-plane librational vibration

William T.S. Cole, Ray S. Fellers, Mark R. Viant, Claude Leforestier, Richard J. Saykally^*

^*Corresponding author for this work

Biosciences

Research output: Contribution to journal › Article › peer-review

Abstract

We report the first high-resolution spectra for the out-of-plane librational vibration in the water dimer. Three vibrational subbands comprising a total of 188 transitions have been measured by diode laser spectroscopy near 500 cm^-1 and assigned to (H₂O)₂ libration-rotation-tunneling eigenstates. The band origin for the K_a = 1 subband is 524 cm^-1. Librational excitation increases the interchange and bifurcation hydrogen bond rearrangement tunneling splittings by factors of 3-5 and 4-40, respectively. Analysis of the rotational constants obtained from a nonlinear least squares fit indicates that additional external perturbations to the energy levels are likely.

Original language	English
Article number	154306
Journal	Journal of Chemical Physics
Volume	143
Issue number	15
DOIs	https://doi.org/10.1063/1.4933116
Publication status	Published - 21 Oct 2015

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© 2015 AIP Publishing LLC.

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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title = "Far-infrared VRT spectroscopy of the water dimer: Characterization of the 20 μ m out-of-plane librational vibration",

abstract = "We report the first high-resolution spectra for the out-of-plane librational vibration in the water dimer. Three vibrational subbands comprising a total of 188 transitions have been measured by diode laser spectroscopy near 500 cm-1 and assigned to (H2O)2 libration-rotation-tunneling eigenstates. The band origin for the Ka = 1 subband is 524 cm-1. Librational excitation increases the interchange and bifurcation hydrogen bond rearrangement tunneling splittings by factors of 3-5 and 4-40, respectively. Analysis of the rotational constants obtained from a nonlinear least squares fit indicates that additional external perturbations to the energy levels are likely.",

author = "Cole, {William T.S.} and Fellers, {Ray S.} and Viant, {Mark R.} and Claude Leforestier and Saykally, {Richard J.}",

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T2 - Characterization of the 20 μ m out-of-plane librational vibration

AU - Cole, William T.S.

AU - Fellers, Ray S.

AU - Viant, Mark R.

AU - Leforestier, Claude

AU - Saykally, Richard J.

PY - 2015/10/21

Y1 - 2015/10/21

N2 - We report the first high-resolution spectra for the out-of-plane librational vibration in the water dimer. Three vibrational subbands comprising a total of 188 transitions have been measured by diode laser spectroscopy near 500 cm-1 and assigned to (H2O)2 libration-rotation-tunneling eigenstates. The band origin for the Ka = 1 subband is 524 cm-1. Librational excitation increases the interchange and bifurcation hydrogen bond rearrangement tunneling splittings by factors of 3-5 and 4-40, respectively. Analysis of the rotational constants obtained from a nonlinear least squares fit indicates that additional external perturbations to the energy levels are likely.

AB - We report the first high-resolution spectra for the out-of-plane librational vibration in the water dimer. Three vibrational subbands comprising a total of 188 transitions have been measured by diode laser spectroscopy near 500 cm-1 and assigned to (H2O)2 libration-rotation-tunneling eigenstates. The band origin for the Ka = 1 subband is 524 cm-1. Librational excitation increases the interchange and bifurcation hydrogen bond rearrangement tunneling splittings by factors of 3-5 and 4-40, respectively. Analysis of the rotational constants obtained from a nonlinear least squares fit indicates that additional external perturbations to the energy levels are likely.

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JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

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ER -

Far-infrared VRT spectroscopy of the water dimer: Characterization of the 20 μ m out-of-plane librational vibration

Abstract

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