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

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Heats of Formation of Medium-Size Organic Compounds from Contemporary Electronic Structure Methods Heats of Formation of Medium-Size Organic Compounds from Contemporary Electronic Structure Methods Item Type Article Authors Minenkov, Yury; Wang, Heng; Wang, Zhandong; Sarathy, Mani; Cavallo, Luigi 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. Eprint version Post-print DOI 10.1021/acs.jctc.7b00335 Publisher American Chemical Society (ACS) Journal Journal of Chemical Theory and Computation Rights This 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. Download date 29/09/2021 06:49:36 Link to Item http://hdl.handle.net/10754/625180 Subscriber access provided by King Abdullah University of Science and Technology Library Article Heats of Formation of Medium-Size Organic Compounds from Contemporary Electronic Structure Methods Yury Minenkov, Heng Wang, Zhandong Wang, S. Mani Sarathy, and Luigi Cavallo J. Chem. Theory Comput., Just Accepted Manuscript • DOI: 10.1021/acs.jctc.7b00335 • Publication Date (Web): 21 Jun 2017 Downloaded from http://pubs.acs.org on July 10, 2017 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts. Journal of Chemical Theory and Computation is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties. Page 1 of 65 Journal of Chemical Theory and Computation 1 2 3 4 5 6 7 8 Heats of Formation of Medium-Size Organic 9 10 11 12 Compounds from Contemporary Electronic 13 14 15 16 Structure Methods 17 18 19 20 21 Yury Minenkov, †,*,a Heng Wang, ‡,a Zhandong Wang, ‡ S. Mani Sarathy,‡,* and Luigi Cavallo †,* 22 23 24 †King Abdullah University of Science and Technology (KAUST), Physical Science and 25 26 27 Engineering Division (PSE), KAUST Catalysis Center (KCC), 23955-6900 Thuwal, Saudi 28 29 Arabia. 30 31 32 ‡ 33 King Abdullah University of Science and Technology (KAUST), Physical Science and 34 35 Engineering Division (PSE), Clean Combustion Research Center (CCRC), 23955-6900 Thuwal, 36 37 Saudi Arabia. 38 39 40 41 42 43 a) 44 Contributed equally to this work. 45 46 47 48 49 50 KEYWORDS: Formation enthalpies, organic molecules, ab initio, DLPNO-CCSD(T), DFT 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment 1 Journal of Chemical Theory and Computation Page 2 of 65 1 2 3 ABSTRACT. Computational electronic structure calculations are routinely undertaken to predict 4 5 6 thermodynamic properties of the various species. However, the application of highly accurate 7 8 wave function theory methods, such as the “gold standard” coupled cluster approach including 9 10 11 single, double and partly triple excitations in perturbative fashion, CCSD(T), to large molecules 12 13 is limited due to high computational cost. In this work, the promising domain based local pair 14 15 natural orbital coupled cluster approach, DLPNO-CCSD(T), has been tested to reproduce 113 16 17 18 accurate formation enthalpies of medium-size molecules (few dozens heavy atoms) important for 19 20 bio- and combustion chemistry via the reaction based Feller-Peterson-Dixon approach. As for 21 22 comparison, 8 density functional theory (B3LYP, B3LYP-D3, PBE0, PBE0-D3, M06, M06-2X, 23 24 25 ωB97X-D3, and ωB97M-V) and MP2-based (B2PLYP-D3, PWPB95-D3, B2T-PLYP, B2T- 26 27 PLYP-D, B2GP-PLYP, DSD-PBEP86-D3, SCS-MP2, and OO-SCS-MP2) methods have been 28 29 tested. The worst performance has been obtained for the standard hybrid DFT functionals, PBE0 30 31 32 (Mean unsigned error (MUE)/ Mean Signed Error (MSE)=9.1/6.0 kcal/mol) and B3LYP 33 34 (MUE/MSE=13.5/-13.3 kcal/mol). An influence of an empirical dispersion correction term on 35 36 37 these functionals performance is not homogenous: B3LYP performance is improved (B3LYP-D3 38 39 (MUE/MSE=6.0/0.8 kcal/mol)) meanwhile PBE0 performance is worse (PBE0-D3 40 41 (MUE/MSE=14.1/13.6 kcal/mol)). The Minnesota functionals, M06 (MUE/MSE=3.8/-2.0 42 43 44 kcal/mol) and M06-2X (MUE/MSE=3.5/3.0 kcal/mol), and recently developed ωB97X-D3 45 46 (MUE/MSE=3.2/0.2 kcal/mol) and ωB97M-V (MUE/MSE=2.2/1.3 kcal/mol) methods provided 47 48 significantly better formation enthalpies. Enthalpies of similar quality can also be obtained from 49 50 51 some double hybrid methods (B2PLYP-D3 (MUE/MSE=4.7/2.0 kcal/mol), PWPB95-D3 52 53 (MUE/MSE=4.3/3.2 kcal/mol), B2T-PLYP (MUE/MSE=4.1/-3.0 kcal/mol) and B2T-PLYP-D 54 55 (MUE/MSE=3.3/1.7 kcal/mol)). The two spin component scaled (SCS) MP2 methods resulted in 56 57 58 59 60 ACS Paragon Plus Environment 2 Page 3 of 65 Journal of Chemical Theory and Computation 1 2 3 even smaller errors (SCS-MP2 (MUE/MSE = 1.9/1.2 kcal/mol) and OO-SCS-MP2 (MUE/MSE 4 5 6 = 1.6/0.1 kcal/mol)). The best performance was found for the frozen core (FC) DLPNO- 7 8 CCSD(T) method with MUE/MSE of 1.6/-1.2 kcal/mol. The performance of the DLPNO- 9 10 11 CCSD(T) method can be further improved by running the post-SCF calculations on the B3LYP 12 13 orbitals: the MUE/MSE for DLPNO-CCSD(T, B3LYP) approximation are 1.2/-0.4 kcal/mol. 14 15 We recommend the DLPNO-CCSD(T, B3LYP) method for the black box applications in 16 17 18 thermodynamics of the medium-size organic molecules when the canonical CCSD(T) 19 20 calculations with the basis sets of the reasonable quality are prohibitively expensive. 21 22 23 24 25 26 27 1. Introduction 28 29 30 Gas phase formation enthalpy (∆Hf) of a chemical substance is a fundamental building block in 31 32 chemical sciences. When combined with standard molar entropies (S°), heat capacities (C ), 33 p 34 35 heats of phase change (∆Htr ), and solvation Gibbs free energies (G s), the formation enthalpies 36 37 can be used to calculate the equilibrium constant via Hess’s Law. In contrast to direct 38 39 experimental measurements, thermodynamic calculations based on heats of formations can be 40 41 42 used to derive the equilibrium constant for every reaction at any conditions. For example, the 43 44 equilibrium constant or the reaction heat of the incomplete burning of graphite (C (gr) + ½ O 2 → 45 46 47 CO) cannot be measured, in principle , since CO 2 will be always formed as side product along 48 49 with CO: only thermodynamic calculations can be used to isolate such a process. Similarly, 50 51 experimentally measuring all the micro-kinetic equilibria of thousands of chemical reactions 52 53 54 occurring inside the bulk of the fuel in a nuclear reactor, or more simply in the combustion 55 56 engines of cars is, at least , challenging; thus, leading to exclusive use of thermodynamic 57 58 59 60 ACS Paragon Plus Environment 3 Journal of Chemical Theory and Computation Page 4 of 65 1 2 3 calculations to model these processes. Results of such modelling are often used to design new 4 5 1-2 3-5 6-8 6 high temperature materials to satisfy the demands of aerospace and nuclear industries, to 7 8 unravel the reaction mechanisms and predict the fuel/oxidant efficiency in combustion 9 10 9-11 11 thermochemistry. For instance, Adiabatic Flame Temperature (AFT) is an important 12 13 combustion property that directly influences other finite rate limited phenomenon, such as 14 15 laminar burning velocity.12 AFT can be measured by experiment or by thermodynamic 16 17 18 calculations requiring enthalpy of formation, entropy, and heat capacities of species. AFT can be 19 20 then used to determine the combustion efficiency and heat transfer.
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