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Title: Active Thermochemical Tables: The Partition Function of Hydroxymethyl (CH 2OH) Revisited

Abstract

The best currently available set of temperature-dependent non-rigid rotor anharmonic oscillator (NRRAO) thermochemical and thermophysical properties of hydroxymethyl radical is presented. The underlying partition function relies on a critically evaluated complement of accurate experimental and theoretical data, and is constructed using a two-pronged strategy that combines contributions from large amplitude motions obtained from direct counts, with contributions from the other internal modes of motion obtained from analytic NRRAO expressions. The contributions from the two strongly coupled large-amplitude motions of CH 2OH, OH torsion and CH 2 wag, are based on energy levels obtained by solving the appropriate two-dimensional projection of a fully-dimensional potential energy surface that was recently obtained at the CCSD(T)/cc-pVTZ level of theory. The contributions of the remaining seven, more rigid, vibrational modes and of the external rotations are captured by NRRAO corrections to the standard rigid rotor harmonic oscillator (RRHO) treatment, which include corrections for vibrational anharmonicities, rotation-vibration interaction, Coriolis effects, and low-temperature. Here, the basic spectroscopic constants needed for the construction of the initial RRHO partition function rely on experimental ground-state rotational constants and the best available experimental fundamentals, additionally complemented by fundamentals obtained from the variational solution of the full-dimensional potential energy surface using amore » recently developed two-component multi-layer Lanczos algorithm.« less

Authors:
 [1];  [2];  [1];  [3]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States); The Univ. of Chicago, Chicago, IL (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1508523
Report Number(s):
BNL-211571-2019-JAAM
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Bross, David H., Yu, Hua -Gen, Harding, Lawrence B., and Ruscic, Branko. Active Thermochemical Tables: The Partition Function of Hydroxymethyl (CH2OH) Revisited. United States: N. p., 2019. Web. doi:10.1021/acs.jpca.9b02295.
Bross, David H., Yu, Hua -Gen, Harding, Lawrence B., & Ruscic, Branko. Active Thermochemical Tables: The Partition Function of Hydroxymethyl (CH2OH) Revisited. United States. doi:10.1021/acs.jpca.9b02295.
Bross, David H., Yu, Hua -Gen, Harding, Lawrence B., and Ruscic, Branko. Thu . "Active Thermochemical Tables: The Partition Function of Hydroxymethyl (CH2OH) Revisited". United States. doi:10.1021/acs.jpca.9b02295.
@article{osti_1508523,
title = {Active Thermochemical Tables: The Partition Function of Hydroxymethyl (CH2OH) Revisited},
author = {Bross, David H. and Yu, Hua -Gen and Harding, Lawrence B. and Ruscic, Branko},
abstractNote = {The best currently available set of temperature-dependent non-rigid rotor anharmonic oscillator (NRRAO) thermochemical and thermophysical properties of hydroxymethyl radical is presented. The underlying partition function relies on a critically evaluated complement of accurate experimental and theoretical data, and is constructed using a two-pronged strategy that combines contributions from large amplitude motions obtained from direct counts, with contributions from the other internal modes of motion obtained from analytic NRRAO expressions. The contributions from the two strongly coupled large-amplitude motions of CH2OH, OH torsion and CH2 wag, are based on energy levels obtained by solving the appropriate two-dimensional projection of a fully-dimensional potential energy surface that was recently obtained at the CCSD(T)/cc-pVTZ level of theory. The contributions of the remaining seven, more rigid, vibrational modes and of the external rotations are captured by NRRAO corrections to the standard rigid rotor harmonic oscillator (RRHO) treatment, which include corrections for vibrational anharmonicities, rotation-vibration interaction, Coriolis effects, and low-temperature. Here, the basic spectroscopic constants needed for the construction of the initial RRHO partition function rely on experimental ground-state rotational constants and the best available experimental fundamentals, additionally complemented by fundamentals obtained from the variational solution of the full-dimensional potential energy surface using a recently developed two-component multi-layer Lanczos algorithm.},
doi = {10.1021/acs.jpca.9b02295},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {4}
}

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This content will become publicly available on April 18, 2020
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