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Title: Near infrared overtone (v OH = 2 ← 0) spectroscopy of Ne–H 2 O clusters

Abstract

Vibrationally state selective overtone spectroscopy and dynamics of weakly bound Ne–H2O complexes (D0(para) = 31.67 cm−1, D0(ortho) = 34.66 cm−1) are reported for the first time, based on near infrared excitation of van der Waals cluster bands correlating with vOH = 2 ← 0 overtone transitions (|02−⟩←|00+⟩ and |02+⟩←|00+⟩) out of the ortho (101) and para (000) internal rotor states of the H2O moiety. Quantum theoretical calculations for nuclear motion on a high level ab initio potential energy surface (CCSD(T)/VnZ-f12 (n = 3,4), corrected for basis set superposition error and extrapolated to the complete basis set limit) are employed for assignment of Σ←Σ,Π←Σ, and Σ←Π infrared bands in the overtone spectra, where Σ(K = 0) and Π (K = 1) represent approximate projections (K) of the body angular momentum along the Ne–H2O internuclear axis. End-over-end tumbling of the ortho Ne–H2O cluster is evident via rotational band contours observed, with band origins and rotational progressions in excellent agreement with ab initio frequency and intensity predictions. A clear Q branch in the corresponding |02+⟩fΠ(111)←eΣ(000) para Ne–H2O spectrum provides evidence for a novel e/f parity-dependent metastability in these weakly bound clusters, in agreement with ab initio bound state calculations and attributable to the symmetry blocking of anmore » energetically allowed channel for internal rotor predissociation. Finally, Boltzmann analysis of the rotational spectra reveals anomalously low jet temperatures (Trot ≈ 4(1) K), which are attributed to “evaporative cooling” of weakly bound Ne–H2O clusters and provide support for similar cooling dynamics in rare gas-tagging studies.« less

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [1]
  1. JILA, National Institute of Standards and Technology, University of Colorado and Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, Colorado 80309, USA
  2. Service de Chimie Quantique et Photophysique, Université Libre de Bruxelles, 50 av. F.D. Roosevelt, CP 160/09, 1050 Brussels, Belgium
  3. Theoretical Chemistry, Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1535300
Alternate Identifier(s):
OSTI ID: 1349363
Grant/Contract Number:  
SC0002123; FG02-09ER16021
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 10; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Physics

Citation Formats

Ziemkiewicz, Michael P., Pluetzer, Christian, Wojcik, Michael, Loreau, Jérôme, van der Avoird, Ad, and Nesbitt, David J. Near infrared overtone (v OH = 2 ← 0) spectroscopy of Ne–H 2 O clusters. United States: N. p., 2017. Web. doi:10.1063/1.4977061.
Ziemkiewicz, Michael P., Pluetzer, Christian, Wojcik, Michael, Loreau, Jérôme, van der Avoird, Ad, & Nesbitt, David J. Near infrared overtone (v OH = 2 ← 0) spectroscopy of Ne–H 2 O clusters. United States. doi:10.1063/1.4977061.
Ziemkiewicz, Michael P., Pluetzer, Christian, Wojcik, Michael, Loreau, Jérôme, van der Avoird, Ad, and Nesbitt, David J. Tue . "Near infrared overtone (v OH = 2 ← 0) spectroscopy of Ne–H 2 O clusters". United States. doi:10.1063/1.4977061. https://www.osti.gov/servlets/purl/1535300.
@article{osti_1535300,
title = {Near infrared overtone (v OH = 2 ← 0) spectroscopy of Ne–H 2 O clusters},
author = {Ziemkiewicz, Michael P. and Pluetzer, Christian and Wojcik, Michael and Loreau, Jérôme and van der Avoird, Ad and Nesbitt, David J.},
abstractNote = {Vibrationally state selective overtone spectroscopy and dynamics of weakly bound Ne–H2O complexes (D0(para) = 31.67 cm−1, D0(ortho) = 34.66 cm−1) are reported for the first time, based on near infrared excitation of van der Waals cluster bands correlating with vOH = 2 ← 0 overtone transitions (|02−⟩←|00+⟩ and |02+⟩←|00+⟩) out of the ortho (101) and para (000) internal rotor states of the H2O moiety. Quantum theoretical calculations for nuclear motion on a high level ab initio potential energy surface (CCSD(T)/VnZ-f12 (n = 3,4), corrected for basis set superposition error and extrapolated to the complete basis set limit) are employed for assignment of Σ←Σ,Π←Σ, and Σ←Π infrared bands in the overtone spectra, where Σ(K = 0) and Π (K = 1) represent approximate projections (K) of the body angular momentum along the Ne–H2O internuclear axis. End-over-end tumbling of the ortho Ne–H2O cluster is evident via rotational band contours observed, with band origins and rotational progressions in excellent agreement with ab initio frequency and intensity predictions. A clear Q branch in the corresponding |02+⟩fΠ(111)←eΣ(000) para Ne–H2O spectrum provides evidence for a novel e/f parity-dependent metastability in these weakly bound clusters, in agreement with ab initio bound state calculations and attributable to the symmetry blocking of an energetically allowed channel for internal rotor predissociation. Finally, Boltzmann analysis of the rotational spectra reveals anomalously low jet temperatures (Trot ≈ 4(1) K), which are attributed to “evaporative cooling” of weakly bound Ne–H2O clusters and provide support for similar cooling dynamics in rare gas-tagging studies.},
doi = {10.1063/1.4977061},
journal = {Journal of Chemical Physics},
number = 10,
volume = 146,
place = {United States},
year = {2017},
month = {3}
}

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Works referenced in this record:

Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis
journal, August 1999

  • Welton, Thomas
  • Chemical Reviews, Vol. 99, Issue 8, p. 2071-2084
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