skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Active Thermochemical Tables: The Partition Function of Hydroxymethyl (CH2OH) Revisited

Abstract

The best currently available set of temperature dependent nonrigid 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. 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 multilayer Lanczos algorithm. The higher-order spectroscopic constants necessary for the NRRAO corrections are extracted from a second-order variational perturbation treatment (VPT2) of the same potential energy surface. The Lanczos solutions of the fully dimensional surface are validated against available experimental data, and the VPT2 results and the solutions of the reduced dimensionality surface are validated both against the Lanczos solutions and available experiments. The NRRAO thermophysical and thermochemical properties, given both in tabular form and as seven- and nine-coefficient NASA polynomials, are compared to previous results. In addition, the latest ATcT values for the enthalpy of formation of CH2OH at 298.15 K (0 K), -16.75 +/- 0.27 kJ/mol (-10.45 +/- 0.27 kJ/ mol), and of other related CHnOm species (n = 0-4, m = 0,1) are reported, together with a plethora of related bond dissociation enthalpies (BDEs), such as the C-H, O-H, and C-O bond dissociation enthalpies of methanol, 402.16 +/- 0.26 kJ/mol (395.61 +/- 0.26 kJ/mol), 440.34 +/- 0.26 kJ/mol (434.86 +/- 0.26 kJ/mol), and 384.85 +/- 0.15 kJ/mol (377.14 +/- 0.15 kJ/mol), respectively, and analogous BDEs for hydroxymethyl, 343.67 +/- 0.37 kJ/mol (339.16 +/- 0.37 kJ/mol), 125.54 0.28 kJ/mol (121.11 +/- 0.28 kJ/mol), and 445.86 +/- 0.29 kJ/mol (438.76 +/- 0.29 kJ/mol), respectively. The reasons governing the alternation between strong and weak sequential H atom BDEs of methanol are also discussed.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1531172
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 123; Journal Issue: 19
Country of Publication:
United States
Language:
English
Subject:
Active Thermochemical Tables; bond dissociation enthalpy; entropy; heat capacity; partition function; thermochemistry

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_1531172,
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 nonrigid 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. 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 multilayer Lanczos algorithm. The higher-order spectroscopic constants necessary for the NRRAO corrections are extracted from a second-order variational perturbation treatment (VPT2) of the same potential energy surface. The Lanczos solutions of the fully dimensional surface are validated against available experimental data, and the VPT2 results and the solutions of the reduced dimensionality surface are validated both against the Lanczos solutions and available experiments. The NRRAO thermophysical and thermochemical properties, given both in tabular form and as seven- and nine-coefficient NASA polynomials, are compared to previous results. In addition, the latest ATcT values for the enthalpy of formation of CH2OH at 298.15 K (0 K), -16.75 +/- 0.27 kJ/mol (-10.45 +/- 0.27 kJ/ mol), and of other related CHnOm species (n = 0-4, m = 0,1) are reported, together with a plethora of related bond dissociation enthalpies (BDEs), such as the C-H, O-H, and C-O bond dissociation enthalpies of methanol, 402.16 +/- 0.26 kJ/mol (395.61 +/- 0.26 kJ/mol), 440.34 +/- 0.26 kJ/mol (434.86 +/- 0.26 kJ/mol), and 384.85 +/- 0.15 kJ/mol (377.14 +/- 0.15 kJ/mol), respectively, and analogous BDEs for hydroxymethyl, 343.67 +/- 0.37 kJ/mol (339.16 +/- 0.37 kJ/mol), 125.54 0.28 kJ/mol (121.11 +/- 0.28 kJ/mol), and 445.86 +/- 0.29 kJ/mol (438.76 +/- 0.29 kJ/mol), respectively. The reasons governing the alternation between strong and weak sequential H atom BDEs of methanol are also discussed.},
doi = {10.1021/acs.jpca.9b02295},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 19,
volume = 123,
place = {United States},
year = {2019},
month = {5}
}