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Title: High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency

Abstract

A number of economical modifications to the high-accuracy extrapolated ab initio thermochemistry (HEAT) model chemistry are evaluated. The two resulting schemes, designated as mHEAT and mHEAT+, are designed for efficient and pragmatic evaluation of molecular energies in systems somewhat larger than can be practically studied by the unapproximated HEAT scheme. It is found that mHEAT+ produces heats of formation with nearly subchemical ± 1 kJ/mol) accuracy at a substantially reduced cost relative to the full scheme. Total atomization energies calculated using the new thermochemical recipes are compared to the results of the HEAT-345(Q) model chemistry, and enthalpies of formation for the three protocols are also compared to Active Thermochemical Tables. Finally, a small selection of transition states is studied using mHEAT and mHEAT+, which illuminates some interesting features of reaction barriers and serves as an initial benchmark of the performance of these model chemistries for chemical kinetics applications.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry
  2. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
  3. Ben-Gurion Univ. of the Negev, Be’er-Sheva (Israel). Dept. of Chemistry
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1559874
Alternate Identifier(s):
OSTI ID: 1525557
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Active Thermochemical Tables; composite method; electronic structure method; thermochemistry

Citation Formats

Thorpe, James H., Lopez, Chris A., Nguyen, Thanh Lam, Baraban, Joshua H., Bross, David H., Ruscic, Branko, and Stanton, John F. High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency. United States: N. p., 2019. Web. doi:10.1063/1.5095937.
Thorpe, James H., Lopez, Chris A., Nguyen, Thanh Lam, Baraban, Joshua H., Bross, David H., Ruscic, Branko, & Stanton, John F. High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency. United States. doi:10.1063/1.5095937.
Thorpe, James H., Lopez, Chris A., Nguyen, Thanh Lam, Baraban, Joshua H., Bross, David H., Ruscic, Branko, and Stanton, John F. Fri . "High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency". United States. doi:10.1063/1.5095937.
@article{osti_1559874,
title = {High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency},
author = {Thorpe, James H. and Lopez, Chris A. and Nguyen, Thanh Lam and Baraban, Joshua H. and Bross, David H. and Ruscic, Branko and Stanton, John F.},
abstractNote = {A number of economical modifications to the high-accuracy extrapolated ab initio thermochemistry (HEAT) model chemistry are evaluated. The two resulting schemes, designated as mHEAT and mHEAT+, are designed for efficient and pragmatic evaluation of molecular energies in systems somewhat larger than can be practically studied by the unapproximated HEAT scheme. It is found that mHEAT+ produces heats of formation with nearly subchemical ± 1 kJ/mol) accuracy at a substantially reduced cost relative to the full scheme. Total atomization energies calculated using the new thermochemical recipes are compared to the results of the HEAT-345(Q) model chemistry, and enthalpies of formation for the three protocols are also compared to Active Thermochemical Tables. Finally, a small selection of transition states is studied using mHEAT and mHEAT+, which illuminates some interesting features of reaction barriers and serves as an initial benchmark of the performance of these model chemistries for chemical kinetics applications.},
doi = {10.1063/1.5095937},
journal = {Journal of Chemical Physics},
number = 22,
volume = 150,
place = {United States},
year = {2019},
month = {6}
}

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