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Title: An Automated Thermochemistry Protocol Based on Explicitly Correlated Coupled-Cluster Theory: The Methyl and Ethyl Peroxy Families

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Missouri Univ. of Science and Technology, Rolla, MO (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Chicago, IL (United States)
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An automated computational thermochemistry protocol based on explicitly correlated coupled-cluster theory was determined to produce highly accurate enthalpies of formation and atomization energies for small- to medium-sized molecular species (3–12 atoms). Each possible source of error was carefully examined, and the sizes of contributions to the total atomization enthalpies were used to generate uncertainty estimates. The protocol was first used to generate total atomization enthalpies for a family of four molecular species exhibiting a variety of charges, multiplicities, and electronic ground states. The new protocol was demonstrated to be in good agreement with the Active Thermochemical Tables database for the four species: the methyl peroxy radical, methoxyoxoniumylidene (methyl peroxy cation), methyl peroxy anion, and methyl hydroperoxide. Updating the Active Thermochemical Tables to include those results yielded significantly improved accuracy for the formation enthalpies of those species. The derived protocol was then used to predict formation enthalpies for the larger ethyl peroxy family of species.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-06CH11357; SC0019740
OSTI ID:
1559535
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 123, Issue 26; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

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An ab initio based full-dimensional potential energy surface for OH + O 2 ⇄ HO 3 and low-lying vibrational levels of HO 3 journal January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Active Thermochemical Tables
thermochemistry