Heats of Formation of Medium-Size Organic Compounds from Contemporary Electronic Structure Methods

Handle URI:
http://hdl.handle.net/10754/625180
Title:
Heats of Formation of Medium-Size Organic Compounds from Contemporary Electronic Structure Methods
Authors:
Minenkov, Yury; Wang, Heng; Wang, Zhandong ( 0000-0003-1535-2319 ) ; Sarathy, Mani ( 0000-0002-3975-6206 ) ; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
Computational electronic structure calculations are routinely undertaken to predict thermodynamic properties of the various species. However, the application of highly accurate wave function theory methods, such as the “gold standard” coupled cluster approach including single, double and partly triple excitations in perturbative fashion, CCSD(T), to large molecules is limited due to high computational cost. In this work, the promising domain based local pair natural orbital coupled cluster approach, DLPNO-CCSD(T), has been tested to reproduce 113 accurate formation enthalpies of medium-size molecules (few dozens heavy atoms) important for bio- and combustion chemistry via the reaction based Feller-Peterson-Dixon approach. As for comparison, 8 density functional theory (B3LYP, B3LYP-D3, PBE0, PBE0-D3, M06, M06-2X, ωB97X-D3, and ωB97M-V) and MP2-based (B2PLYP-D3, PWPB95-D3, B2T-PLYP, B2T-PLYP-D, B2GP-PLYP, DSD-PBEP86-D3, SCS-MP2, and OO-SCS-MP2) methods have been tested. The worst performance has been obtained for the standard hybrid DFT functionals, PBE0 (Mean unsigned error (MUE)/ Mean Signed Error (MSE)=9.1/6.0 kcal/mol) and B3LYP (MUE/MSE=13.5/-13.3 kcal/mol). An influence of an empirical dispersion correction term on these functionals performance is not homogenous: B3LYP performance is improved (B3LYP-D3 (MUE/MSE=6.0/0.8 kcal/mol)) meanwhile PBE0 performance is worse (PBE0-D3 (MUE/MSE=14.1/13.6 kcal/mol)). The Minnesota functionals, M06 (MUE/MSE=3.8/-2.0 kcal/mol) and M06-2X (MUE/MSE=3.5/3.0 kcal/mol), and recently developed ωB97X-D3 (MUE/MSE=3.2/0.2 kcal/mol) and ωB97M-V (MUE/MSE=2.2/1.3 kcal/mol) methods provided significantly better formation enthalpies. Enthalpies of similar quality can also be obtained from some double hybrid methods (B2PLYP-D3 (MUE/MSE=4.7/2.0 kcal/mol), PWPB95-D3 (MUE/MSE=4.3/3.2 kcal/mol), B2T-PLYP (MUE/MSE=4.1/-3.0 kcal/mol) and B2T-PLYP-D (MUE/MSE=3.3/1.7 kcal/mol)). The two spin component scaled (SCS) MP2 methods resulted in even smaller errors (SCS-MP2 (MUE/MSE = 1.9/1.2 kcal/mol) and OO-SCS-MP2 (MUE/MSE = 1.6/0.1 kcal/mol)). The best performance was found for the frozen core (FC) DLPNO-CCSD(T) method with MUE/MSE of 1.6/-1.2 kcal/mol. The performance of the DLPNO-CCSD(T) method can be further improved by running the post-SCF calculations on the B3LYP orbitals: the MUE/MSE for DLPNO-CCSD(T, B3LYP) approximation are 1.2/-0.4 kcal/mol. We recommend the DLPNO-CCSD(T, B3LYP) method for the black box applications in thermodynamics of the medium-size organic molecules when the canonical CCSD(T) calculations with the basis sets of the reasonable quality are prohibitively expensive.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Clean Combustion Research Center
Citation:
Minenkov Y, Wang H, Wang Z, Sarathy SM, Cavallo L (2017) Heats of Formation of Medium-Sized Organic Compounds from Contemporary Electronic Structure Methods. Journal of Chemical Theory and Computation. Available: http://dx.doi.org/10.1021/acs.jctc.7b00335.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of Chemical Theory and Computation
Issue Date:
21-Jun-2017
DOI:
10.1021/acs.jctc.7b00335
Type:
Article
ISSN:
1549-9618; 1549-9626
Sponsors:
The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST). For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.jctc.7b00335
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC); Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorMinenkov, Yuryen
dc.contributor.authorWang, Hengen
dc.contributor.authorWang, Zhandongen
dc.contributor.authorSarathy, Manien
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2017-07-12T07:20:54Z-
dc.date.available2017-07-12T07:20:54Z-
dc.date.issued2017-06-21en
dc.identifier.citationMinenkov Y, Wang H, Wang Z, Sarathy SM, Cavallo L (2017) Heats of Formation of Medium-Sized Organic Compounds from Contemporary Electronic Structure Methods. Journal of Chemical Theory and Computation. Available: http://dx.doi.org/10.1021/acs.jctc.7b00335.en
dc.identifier.issn1549-9618en
dc.identifier.issn1549-9626en
dc.identifier.doi10.1021/acs.jctc.7b00335en
dc.identifier.urihttp://hdl.handle.net/10754/625180-
dc.description.abstractComputational electronic structure calculations are routinely undertaken to predict thermodynamic properties of the various species. However, the application of highly accurate wave function theory methods, such as the “gold standard” coupled cluster approach including single, double and partly triple excitations in perturbative fashion, CCSD(T), to large molecules is limited due to high computational cost. In this work, the promising domain based local pair natural orbital coupled cluster approach, DLPNO-CCSD(T), has been tested to reproduce 113 accurate formation enthalpies of medium-size molecules (few dozens heavy atoms) important for bio- and combustion chemistry via the reaction based Feller-Peterson-Dixon approach. As for comparison, 8 density functional theory (B3LYP, B3LYP-D3, PBE0, PBE0-D3, M06, M06-2X, ωB97X-D3, and ωB97M-V) and MP2-based (B2PLYP-D3, PWPB95-D3, B2T-PLYP, B2T-PLYP-D, B2GP-PLYP, DSD-PBEP86-D3, SCS-MP2, and OO-SCS-MP2) methods have been tested. The worst performance has been obtained for the standard hybrid DFT functionals, PBE0 (Mean unsigned error (MUE)/ Mean Signed Error (MSE)=9.1/6.0 kcal/mol) and B3LYP (MUE/MSE=13.5/-13.3 kcal/mol). An influence of an empirical dispersion correction term on these functionals performance is not homogenous: B3LYP performance is improved (B3LYP-D3 (MUE/MSE=6.0/0.8 kcal/mol)) meanwhile PBE0 performance is worse (PBE0-D3 (MUE/MSE=14.1/13.6 kcal/mol)). The Minnesota functionals, M06 (MUE/MSE=3.8/-2.0 kcal/mol) and M06-2X (MUE/MSE=3.5/3.0 kcal/mol), and recently developed ωB97X-D3 (MUE/MSE=3.2/0.2 kcal/mol) and ωB97M-V (MUE/MSE=2.2/1.3 kcal/mol) methods provided significantly better formation enthalpies. Enthalpies of similar quality can also be obtained from some double hybrid methods (B2PLYP-D3 (MUE/MSE=4.7/2.0 kcal/mol), PWPB95-D3 (MUE/MSE=4.3/3.2 kcal/mol), B2T-PLYP (MUE/MSE=4.1/-3.0 kcal/mol) and B2T-PLYP-D (MUE/MSE=3.3/1.7 kcal/mol)). The two spin component scaled (SCS) MP2 methods resulted in even smaller errors (SCS-MP2 (MUE/MSE = 1.9/1.2 kcal/mol) and OO-SCS-MP2 (MUE/MSE = 1.6/0.1 kcal/mol)). The best performance was found for the frozen core (FC) DLPNO-CCSD(T) method with MUE/MSE of 1.6/-1.2 kcal/mol. The performance of the DLPNO-CCSD(T) method can be further improved by running the post-SCF calculations on the B3LYP orbitals: the MUE/MSE for DLPNO-CCSD(T, B3LYP) approximation are 1.2/-0.4 kcal/mol. We recommend the DLPNO-CCSD(T, B3LYP) method for the black box applications in thermodynamics of the medium-size organic molecules when the canonical CCSD(T) calculations with the basis sets of the reasonable quality are prohibitively expensive.en
dc.description.sponsorshipThe research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST). For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jctc.7b00335en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jctc.7b00335.en
dc.titleHeats of Formation of Medium-Size Organic Compounds from Contemporary Electronic Structure Methodsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentClean Combustion Research Centeren
dc.identifier.journalJournal of Chemical Theory and Computationen
dc.eprint.versionPost-printen
kaust.authorMinenkov, Yuryen
kaust.authorWang, Hengen
kaust.authorWang, Zhandongen
kaust.authorSarathy, Manien
kaust.authorCavallo, Luigien
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.