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Title: An Extended Group Additivity Method for Polycyclic Thermochemistry Estimation: AN EXTENDED GROUP ADDITIVITY METHOD FOR POLYCYCLIC THERMOCHEMISTRY ESTIMATION

Abstract

Automatic kinetic mechanism generation, virtual high-throughput screening, and automatic transition state search are currently trending applications requiring exploration ofa large molecule space. Large-scale search requires fast and accurate estimation of molecules’ properties of interest, such as thermochemistry. Existing approaches are not satisfactory for large polycyclic molecules: considering the number of molecules being screened, quantum chemistry (even cheap density functional theory methods) can be computationally expensive, and group additivity, though fast, is not sufficiently accurate. This paper provides a fast and moderately accurate alternative by proposing a polycyclic thermochemistry estimation method that extends the group additivity method with two additional algorithms: similarity match and bicyclic decomposition. It significantly reduces Hf(298 K) estimation error from over 60 kcal/mol (group additivity method) to around 5 kcal/mol, Cp(298 K) error from 9 to 1 cal/mol/K,and S(298 K) error from 70 to 7 cal/mol/K. This method also works well for heteroatomic poly-cyclics. A web application for estimating thermochemistry by this method is made available at http://rmg.mit.edu/moleculesearch.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Massachusetts Institute of Technology, Cambridge, MA (United States). Department of Chemical Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory, Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC).
Sponsoring Org.:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21)
OSTI Identifier:
1461668
DOE Contract Number:  
SC0014901; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
International Journal of Chemical Kinetics
Additional Journal Information:
Journal Volume: 50; Journal Issue: 4; Journal ID: ISSN 0538-8066
Publisher:
Wiley
Country of Publication:
United States
Language:
English

Citation Formats

Han, Kehang, Jamal, Adeel, Grambow, Colin A., Buras, Zachary J., and Green, William H. An Extended Group Additivity Method for Polycyclic Thermochemistry Estimation: AN EXTENDED GROUP ADDITIVITY METHOD FOR POLYCYCLIC THERMOCHEMISTRY ESTIMATION. United States: N. p., 2018. Web. doi:10.1002/kin.21158.
Han, Kehang, Jamal, Adeel, Grambow, Colin A., Buras, Zachary J., & Green, William H. An Extended Group Additivity Method for Polycyclic Thermochemistry Estimation: AN EXTENDED GROUP ADDITIVITY METHOD FOR POLYCYCLIC THERMOCHEMISTRY ESTIMATION. United States. doi:10.1002/kin.21158.
Han, Kehang, Jamal, Adeel, Grambow, Colin A., Buras, Zachary J., and Green, William H. Thu . "An Extended Group Additivity Method for Polycyclic Thermochemistry Estimation: AN EXTENDED GROUP ADDITIVITY METHOD FOR POLYCYCLIC THERMOCHEMISTRY ESTIMATION". United States. doi:10.1002/kin.21158.
@article{osti_1461668,
title = {An Extended Group Additivity Method for Polycyclic Thermochemistry Estimation: AN EXTENDED GROUP ADDITIVITY METHOD FOR POLYCYCLIC THERMOCHEMISTRY ESTIMATION},
author = {Han, Kehang and Jamal, Adeel and Grambow, Colin A. and Buras, Zachary J. and Green, William H.},
abstractNote = {Automatic kinetic mechanism generation, virtual high-throughput screening, and automatic transition state search are currently trending applications requiring exploration ofa large molecule space. Large-scale search requires fast and accurate estimation of molecules’ properties of interest, such as thermochemistry. Existing approaches are not satisfactory for large polycyclic molecules: considering the number of molecules being screened, quantum chemistry (even cheap density functional theory methods) can be computationally expensive, and group additivity, though fast, is not sufficiently accurate. This paper provides a fast and moderately accurate alternative by proposing a polycyclic thermochemistry estimation method that extends the group additivity method with two additional algorithms: similarity match and bicyclic decomposition. It significantly reduces Hf(298 K) estimation error from over 60 kcal/mol (group additivity method) to around 5 kcal/mol, Cp(298 K) error from 9 to 1 cal/mol/K,and S(298 K) error from 70 to 7 cal/mol/K. This method also works well for heteroatomic poly-cyclics. A web application for estimating thermochemistry by this method is made available at http://rmg.mit.edu/moleculesearch.},
doi = {10.1002/kin.21158},
journal = {International Journal of Chemical Kinetics},
issn = {0538-8066},
number = 4,
volume = 50,
place = {United States},
year = {2018},
month = {2}
}