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Title: W4 theory for computational thermochemistry : in pursuit of confident sub-kJ/mol predictions.

Abstract

In an attempt to improve on our earlier W3 theory [A. D. Boese et al., J. Chem. Phys. 120, 4129 (2004)] we consider such refinements as more accurate estimates for the contribution of connected quadruple excitations ({cflx T}{sub 4}), inclusion of connected quintuple excitations ({cflx T}{sub 5}), diagonal Born-Oppenheimer corrections (DBOC), and improved basis set extrapolation procedures. Revised experimental data for validation purposes were obtained from the latest version of the Active Thermochemical Tables thermochemical network. The recent CCSDT(Q) method offers a cost-effective way of estimating {cflx T}{sub 4} but is insufficient by itself if the molecule exhibits some nondynamical correlation. The latter considerably slows down basis set convergence for {cflx T}{sub 4}, and anomalous basis set convergence in highly polar systems makes two-point extrapolation procedures unusable. However, we found that the CCSDTQ-CCSDT(Q) difference converges quite rapidly with the basis set, and that the formula 1.10[CCSDT(Q)/cc-pVTZ+CCSDTQ/cc-pVDZ-CCSDT(Q)/cc-pVDZ] offers a very reliable as well as fairly cost-effective estimate of the basis set limit {cflx T}{sub 4} contribution. The {cflx T}{sub 5} contribution converges very rapidly with the basis set, and even a simple double-zeta basis set appears to be adequate. The largest {cflx T}{sub 5} contribution found in the present work ismore » on the order of 0.5 kcal/mol (for ozone). DBOCs are significant at the 0.1 kcal/mol level in hydride systems. Post-CCSD(T) contributions to the core-valence correlation energy are only significant at that level in systems with severe nondynamical correlation effects. Based on the accumulated experience, a new computational thermochemistry protocol for first- and second-row main-group systems, to be known as W4 theory, is proposed. Its computational cost is not insurmountably higher than that of the earlier W3 theory, while performance is markedly superior. Our W4 atomization energies for a number of key species are in excellent agreement (better than 0.1 kcal/mol on average, 95% confidence intervals narrower than 1 kJ/mol) with the latest experimental data obtained from Active Thermochemical Tables. Lower-cost variants are proposed: the sequence W1 {yields} W2.2 {yields} 3.2 {yields} W4lite {yields} W4 is proposed as a converging hierarchy of computational thermochemistry methods. A simple a priori estimate for the importance of post-CCSD(T) correlation contributions (and hence a pessimistic estimate for the error in a W2-type calculation) is proposed.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); FOR
OSTI Identifier:
939550
Report Number(s):
ANL/CHM/JA-56933
Journal ID: ISSN 0021-9606; JCPSA6; TRN: US200823%%149
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Chem. Phys.; Journal Volume: 125; Journal Issue: 2006
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 97; EXCITATION; OZONE; HYDRIDES; ATOMIZATION; REACTION HEAT; CALCULATION METHODS

Citation Formats

Karton, A., Rabinovich, E., Martin, J. M. L., Ruscic, B., Chemistry, and Weizmann Institute of Science. W4 theory for computational thermochemistry : in pursuit of confident sub-kJ/mol predictions.. United States: N. p., 2006. Web. doi:10.1063/1.2348881.
Karton, A., Rabinovich, E., Martin, J. M. L., Ruscic, B., Chemistry, & Weizmann Institute of Science. W4 theory for computational thermochemistry : in pursuit of confident sub-kJ/mol predictions.. United States. doi:10.1063/1.2348881.
Karton, A., Rabinovich, E., Martin, J. M. L., Ruscic, B., Chemistry, and Weizmann Institute of Science. Sun . "W4 theory for computational thermochemistry : in pursuit of confident sub-kJ/mol predictions.". United States. doi:10.1063/1.2348881.
@article{osti_939550,
title = {W4 theory for computational thermochemistry : in pursuit of confident sub-kJ/mol predictions.},
author = {Karton, A. and Rabinovich, E. and Martin, J. M. L. and Ruscic, B. and Chemistry and Weizmann Institute of Science},
abstractNote = {In an attempt to improve on our earlier W3 theory [A. D. Boese et al., J. Chem. Phys. 120, 4129 (2004)] we consider such refinements as more accurate estimates for the contribution of connected quadruple excitations ({cflx T}{sub 4}), inclusion of connected quintuple excitations ({cflx T}{sub 5}), diagonal Born-Oppenheimer corrections (DBOC), and improved basis set extrapolation procedures. Revised experimental data for validation purposes were obtained from the latest version of the Active Thermochemical Tables thermochemical network. The recent CCSDT(Q) method offers a cost-effective way of estimating {cflx T}{sub 4} but is insufficient by itself if the molecule exhibits some nondynamical correlation. The latter considerably slows down basis set convergence for {cflx T}{sub 4}, and anomalous basis set convergence in highly polar systems makes two-point extrapolation procedures unusable. However, we found that the CCSDTQ-CCSDT(Q) difference converges quite rapidly with the basis set, and that the formula 1.10[CCSDT(Q)/cc-pVTZ+CCSDTQ/cc-pVDZ-CCSDT(Q)/cc-pVDZ] offers a very reliable as well as fairly cost-effective estimate of the basis set limit {cflx T}{sub 4} contribution. The {cflx T}{sub 5} contribution converges very rapidly with the basis set, and even a simple double-zeta basis set appears to be adequate. The largest {cflx T}{sub 5} contribution found in the present work is on the order of 0.5 kcal/mol (for ozone). DBOCs are significant at the 0.1 kcal/mol level in hydride systems. Post-CCSD(T) contributions to the core-valence correlation energy are only significant at that level in systems with severe nondynamical correlation effects. Based on the accumulated experience, a new computational thermochemistry protocol for first- and second-row main-group systems, to be known as W4 theory, is proposed. Its computational cost is not insurmountably higher than that of the earlier W3 theory, while performance is markedly superior. Our W4 atomization energies for a number of key species are in excellent agreement (better than 0.1 kcal/mol on average, 95% confidence intervals narrower than 1 kJ/mol) with the latest experimental data obtained from Active Thermochemical Tables. Lower-cost variants are proposed: the sequence W1 {yields} W2.2 {yields} 3.2 {yields} W4lite {yields} W4 is proposed as a converging hierarchy of computational thermochemistry methods. A simple a priori estimate for the importance of post-CCSD(T) correlation contributions (and hence a pessimistic estimate for the error in a W2-type calculation) is proposed.},
doi = {10.1063/1.2348881},
journal = {J. Chem. Phys.},
number = 2006,
volume = 125,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}
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