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Title: Nuclear spin/parity dependent spectroscopy and predissociation dynamics in v OH = 2 ← 0 overtone excited Ne–H 2O clusters: Theory and experiment

Abstract

Vibrationally state selective overtone spectroscopy and state- and nuclear spin-dependent predissociation dynamics of weakly bound ortho- and para-Ne–H 2O complexes (D 0(ortho) = 34.66 cm -1 and D 0(para) = 31.67 cm -1) are reported, based on near-infrared excitation of van der Waals cluster bands correlating with v OH = 2 ← 0 overtone transitions (|02 -⟩ and |02 +⟩) out of the ortho (101) and para (000) internal rotor states of the H 2O moiety. Quantum theoretical calculations for nuclear motion on a high level potential energy surface [CCSD(T)/VnZf12 (n = 3, 4)], corrected for basis set superposition error and extrapolated to the complete basis set (CBS) limit, are employed to successfully predict and assign Π–Σ, Σ–Σ, and Σ–Π infrared bands in the spectra, where Σ or Π represent approximate projections of the body-fixed H 2O angular momentum along the Ne–H 2O internuclear axis. IR-UV pump-probe experimental capabilities permit real-time measurements of the vibrational predissociation dynamics, which indicate facile intramolecular vibrational energy transfer from the H 2O v OH = 2 overtone vibrations into the VdWs (van der Waals) dissociation coordinate on the τprediss = 15-25 ns time scale. Whereas all predicted strong transitions in the ortho-Ne–H 2O complexesmore » are readily detected and assigned, vibrationally mediated photolysis spectra for the corresponding para-Ne–H 2O bands are surprisingly absent despite ab initio predictions of Q-branch intensities with S/N > 20-40. Such behavior signals the presence of highly selective nuclear spin ortho-para predissociation dynamics in the upper state, for which we offer a simple mechanism based on Ne-atom mediated intramolecular vibrational relaxation in the H 2O subunit (i.e., |02 ±⟩ → {|01 ±⟩ v 2 = 2}), which is confirmed by the ab initio energy level predictions and the nascent OH rotational (N), spin orbit (Π 1/2,3/2), and lambda doublet product distributions.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [5]
  1. Analog Devices, Inc., Golden, CO (United States)
  2. West Pharmaceuticals Services Deutschland GmbH & Co. KG, Eschweiler (Germany)
  3. Univ. Libre de Bruxelles, Brussels (Belgium). Service de Chimie Quantique et Photophysique
  4. Radboud Univ. Nijmegen, Nijmegen (The Netherlands). Theoretical Chemistry, Inst. for Molecules and Materials
  5. Univ. of Colorado, Boulder, CO (United States). JILA, National Inst. of Standards and Technology, and Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1512940
Alternate Identifier(s):
OSTI ID: 1410876
Grant/Contract Number:  
SC0002123; FG02-09ER16021
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 21; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English

Citation Formats

Ziemkiewicz, Michael P., Pluetzer, Christian, Loreau, Jérôme, van der Avoird, Ad, and Nesbitt, David J. Nuclear spin/parity dependent spectroscopy and predissociation dynamics in vOH = 2 ← 0 overtone excited Ne–H2O clusters: Theory and experiment. United States: N. p., 2017. Web. doi:10.1063/1.5001335.
Ziemkiewicz, Michael P., Pluetzer, Christian, Loreau, Jérôme, van der Avoird, Ad, & Nesbitt, David J. Nuclear spin/parity dependent spectroscopy and predissociation dynamics in vOH = 2 ← 0 overtone excited Ne–H2O clusters: Theory and experiment. United States. doi:10.1063/1.5001335.
Ziemkiewicz, Michael P., Pluetzer, Christian, Loreau, Jérôme, van der Avoird, Ad, and Nesbitt, David J. Thu . "Nuclear spin/parity dependent spectroscopy and predissociation dynamics in vOH = 2 ← 0 overtone excited Ne–H2O clusters: Theory and experiment". United States. doi:10.1063/1.5001335. https://www.osti.gov/servlets/purl/1512940.
@article{osti_1512940,
title = {Nuclear spin/parity dependent spectroscopy and predissociation dynamics in vOH = 2 ← 0 overtone excited Ne–H2O clusters: Theory and experiment},
author = {Ziemkiewicz, Michael P. and Pluetzer, Christian and Loreau, Jérôme and van der Avoird, Ad and Nesbitt, David J.},
abstractNote = {Vibrationally state selective overtone spectroscopy and state- and nuclear spin-dependent predissociation dynamics of weakly bound ortho- and para-Ne–H2O complexes (D0(ortho) = 34.66 cm-1 and D0(para) = 31.67 cm-1) are reported, based on near-infrared excitation of van der Waals cluster bands correlating with vOH = 2 ← 0 overtone transitions (|02-⟩ and |02+⟩) 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 potential energy surface [CCSD(T)/VnZf12 (n = 3, 4)], corrected for basis set superposition error and extrapolated to the complete basis set (CBS) limit, are employed to successfully predict and assign Π–Σ, Σ–Σ, and Σ–Π infrared bands in the spectra, where Σ or Π represent approximate projections of the body-fixed H2O angular momentum along the Ne–H2O internuclear axis. IR-UV pump-probe experimental capabilities permit real-time measurements of the vibrational predissociation dynamics, which indicate facile intramolecular vibrational energy transfer from the H2O vOH = 2 overtone vibrations into the VdWs (van der Waals) dissociation coordinate on the τprediss = 15-25 ns time scale. Whereas all predicted strong transitions in the ortho-Ne–H2O complexes are readily detected and assigned, vibrationally mediated photolysis spectra for the corresponding para-Ne–H2O bands are surprisingly absent despite ab initio predictions of Q-branch intensities with S/N > 20-40. Such behavior signals the presence of highly selective nuclear spin ortho-para predissociation dynamics in the upper state, for which we offer a simple mechanism based on Ne-atom mediated intramolecular vibrational relaxation in the H2O subunit (i.e., |02±⟩ → {|01±⟩ v2 = 2}), which is confirmed by the ab initio energy level predictions and the nascent OH rotational (N), spin orbit (Π1/2,3/2), and lambda doublet product distributions.},
doi = {10.1063/1.5001335},
journal = {Journal of Chemical Physics},
number = 21,
volume = 147,
place = {United States},
year = {2017},
month = {12}
}

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