Far infrared VRT spectroscopy of two water trimer isotopomers vibrationally averaged structures and rearrangement dynamics

K. Liu; M. G. Brown; M. R. Viant; J. D. Cruzan; R. J. Saykally

doi:10.1080/002689796173246

Far infrared VRT spectroscopy of two water trimer isotopomers vibrationally averaged structures and rearrangement dynamics

K. Liu, M. G. Brown, M. R. Viant, J. D. Cruzan, R. J. Saykally

Biosciences

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

Abstract

We report the measurement of far-infrared vibration–rotation tunnelling parallel bands of two partially deuterated water trimer isotopomers: (D₂O)₂DOH and (H₂O)₂DOH at 97•2607 cm^-1 and ∼ 86 cm^-1, respectively. The hydrogen bond rearrangement dynamics of the two mixed trimers can be described by the simplified molecular symmetry G₈, which accounts for both the flipping and bifurcation tunnelling motions previously established for (H₂O)₃ and (D₂O)₃. The observed donor tunnelling quartet, rather than triplet, splitting indicates that the two homogeneous monomers (D₂O or H₂O) in each mixed trimer experience slightly different environments. Vibrationally averaged structures of (H₂O)₃, (D₂O)₃, and (D₂O)₂DOH were examined in a Monte Carlo simulation of the out-of-plane flipping motions of the free atoms. The simulation addresses both the symmetric top behaviour and the negative zero-point inertial defect for (H₂O)₃ and (D₂O)₃, which were insufficiently counted in all previous structure models. The average ground state O—O separations, which are correlated to other angular coordinates, were determined to be 2•84±0•01 Å for all three species. The simulated difference in hydrogen bond nonlinearity also supports the inequivalency of the two homogeneous mono mers The structural simulation shows that the unique H in (D₂O)₂DOH is free, while a torsional analysis suggests the unique D in (H₂O)₂DOH is bound within the cyclic ring. Both bands can be assigned to the pseudorotational transitions which correlate to those found in the pure trimers.

Original language	English
Pages (from-to)	1373-1396
Number of pages	24
Journal	Molecular Physics
Volume	89
Issue number	5
DOIs	https://doi.org/10.1080/002689796173246
Publication status	Published - 1 Dec 1996

Bibliographical note

Funding Information:
This work was supported by the Experimental Physical Chemistry Program of the NationalScienceFoundation(Grantg CHE-9424482).M.R.V.thankstheRoyal Commission for the Exhibition of 1851 for a postdoctoral research fellowship.

ASJC Scopus subject areas

Biophysics
Molecular Biology
Condensed Matter Physics
Physical and Theoretical Chemistry

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10.1080/002689796173246

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@article{9df77819ada941fdab348e7df30b3a75,

title = "Far infrared VRT spectroscopy of two water trimer isotopomers vibrationally averaged structures and rearrangement dynamics",

abstract = "We report the measurement of far-infrared vibration–rotation tunnelling parallel bands of two partially deuterated water trimer isotopomers: (D2O)2DOH and (H2O)2DOH at 97•2607 cm-1 and ∼ 86 cm-1, respectively. The hydrogen bond rearrangement dynamics of the two mixed trimers can be described by the simplified molecular symmetry G8, which accounts for both the flipping and bifurcation tunnelling motions previously established for (H2O)3 and (D2O)3. The observed donor tunnelling quartet, rather than triplet, splitting indicates that the two homogeneous monomers (D2O or H2O) in each mixed trimer experience slightly different environments. Vibrationally averaged structures of (H2O)3, (D2O)3, and (D2O)2DOH were examined in a Monte Carlo simulation of the out-of-plane flipping motions of the free atoms. The simulation addresses both the symmetric top behaviour and the negative zero-point inertial defect for (H2O)3 and (D2O)3, which were insufficiently counted in all previous structure models. The average ground state O—O separations, which are correlated to other angular coordinates, were determined to be 2•84±0•01 {\AA} for all three species. The simulated difference in hydrogen bond nonlinearity also supports the inequivalency of the two homogeneous mono mers The structural simulation shows that the unique H in (D2O)2DOH is free, while a torsional analysis suggests the unique D in (H2O)2DOH is bound within the cyclic ring. Both bands can be assigned to the pseudorotational transitions which correlate to those found in the pure trimers.",

author = "K. Liu and Brown, {M. G.} and Viant, {M. R.} and Cruzan, {J. D.} and Saykally, {R. J.}",

note = "Funding Information: This work was supported by the Experimental Physical Chemistry Program of the NationalScienceFoundation(Grantg CHE-9424482).M.R.V.thankstheRoyal Commission for the Exhibition of 1851 for a postdoctoral research fellowship.",

year = "1996",

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doi = "10.1080/002689796173246",

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T1 - Far infrared VRT spectroscopy of two water trimer isotopomers vibrationally averaged structures and rearrangement dynamics

AU - Liu, K.

AU - Brown, M. G.

AU - Viant, M. R.

AU - Cruzan, J. D.

AU - Saykally, R. J.

N1 - Funding Information: This work was supported by the Experimental Physical Chemistry Program of the NationalScienceFoundation(Grantg CHE-9424482).M.R.V.thankstheRoyal Commission for the Exhibition of 1851 for a postdoctoral research fellowship.

PY - 1996/12/1

Y1 - 1996/12/1

N2 - We report the measurement of far-infrared vibration–rotation tunnelling parallel bands of two partially deuterated water trimer isotopomers: (D2O)2DOH and (H2O)2DOH at 97•2607 cm-1 and ∼ 86 cm-1, respectively. The hydrogen bond rearrangement dynamics of the two mixed trimers can be described by the simplified molecular symmetry G8, which accounts for both the flipping and bifurcation tunnelling motions previously established for (H2O)3 and (D2O)3. The observed donor tunnelling quartet, rather than triplet, splitting indicates that the two homogeneous monomers (D2O or H2O) in each mixed trimer experience slightly different environments. Vibrationally averaged structures of (H2O)3, (D2O)3, and (D2O)2DOH were examined in a Monte Carlo simulation of the out-of-plane flipping motions of the free atoms. The simulation addresses both the symmetric top behaviour and the negative zero-point inertial defect for (H2O)3 and (D2O)3, which were insufficiently counted in all previous structure models. The average ground state O—O separations, which are correlated to other angular coordinates, were determined to be 2•84±0•01 Å for all three species. The simulated difference in hydrogen bond nonlinearity also supports the inequivalency of the two homogeneous mono mers The structural simulation shows that the unique H in (D2O)2DOH is free, while a torsional analysis suggests the unique D in (H2O)2DOH is bound within the cyclic ring. Both bands can be assigned to the pseudorotational transitions which correlate to those found in the pure trimers.

AB - We report the measurement of far-infrared vibration–rotation tunnelling parallel bands of two partially deuterated water trimer isotopomers: (D2O)2DOH and (H2O)2DOH at 97•2607 cm-1 and ∼ 86 cm-1, respectively. The hydrogen bond rearrangement dynamics of the two mixed trimers can be described by the simplified molecular symmetry G8, which accounts for both the flipping and bifurcation tunnelling motions previously established for (H2O)3 and (D2O)3. The observed donor tunnelling quartet, rather than triplet, splitting indicates that the two homogeneous monomers (D2O or H2O) in each mixed trimer experience slightly different environments. Vibrationally averaged structures of (H2O)3, (D2O)3, and (D2O)2DOH were examined in a Monte Carlo simulation of the out-of-plane flipping motions of the free atoms. The simulation addresses both the symmetric top behaviour and the negative zero-point inertial defect for (H2O)3 and (D2O)3, which were insufficiently counted in all previous structure models. The average ground state O—O separations, which are correlated to other angular coordinates, were determined to be 2•84±0•01 Å for all three species. The simulated difference in hydrogen bond nonlinearity also supports the inequivalency of the two homogeneous mono mers The structural simulation shows that the unique H in (D2O)2DOH is free, while a torsional analysis suggests the unique D in (H2O)2DOH is bound within the cyclic ring. Both bands can be assigned to the pseudorotational transitions which correlate to those found in the pure trimers.

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JO - Molecular Physics

JF - Molecular Physics

IS - 5

ER -

Far infrared VRT spectroscopy of two water trimer isotopomers vibrationally averaged structures and rearrangement dynamics

Abstract

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