Efficient DLPNO–CCSD(T)-Based Estimation of Formation Enthalpies for C-, H-, O-, and N-Containing Closed-Shell Compounds Validated Against Critically Evaluated Experimental Data

Published

May 17, 2017

Author(s)

Eugene Paulechka, Andrei F. Kazakov

Abstract

An accurate and cost-efficient methodology for the estimation of the enthalpies of formation for closed-shell compounds composed of C, H, O, and N atoms is presented and validated against critically evaluated experimental data. The computational efficiency is achieved through the use of the resolution-of-identity (RI) and domain-based local pair-natural orbital coupled cluster (DLPNO–CCSD(T)) approximations, which results in a drastic reduction in both the computational cost and the number of necessary steps for a composite quantum chemical method. The expanded uncertainty for the proposed methodology evaluated using a data set of 45 thoroughly vetted experimental values for molecules containing up to 12 heavy atoms is about 3 kJ·mol–1, competitive with those of typical calorimetric measurements. For the compounds within the stated scope, the methodology is shown to be superior to a representative, more general, and widely used composite quantum chemical method, G4.

Citation

Journal of Physical Chemistry A

Volume

121

Issue

22

Pub Type

Journals

Download Paper

https://doi.org/10.1021/acs.jpca.7b03195

Local Download

Keywords

enthalpy of formation, ab initio, DLPNO-CCSD(T)

Citation

Paulechka, E. and Kazakov, A. (2017), Efficient DLPNO–CCSD(T)-Based Estimation of Formation Enthalpies for C-, H-, O-, and N-Containing Closed-Shell Compounds Validated Against Critically Evaluated Experimental Data, Journal of Physical Chemistry A, [online], https://doi.org/10.1021/acs.jpca.7b03195, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=922435 (Accessed October 7, 2025)