W4Λ: Leveraging Λ Coupled-Cluster for Accurate Computational Thermochemistry Approaches
Open Access
- 24 February 2024
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 128 (9) , 1715-1724
Abstract
High-accuracy composite wave function methods like Weizmann-4 (W4) theory, high-accuracy extrapolated ab initio thermochemistry (HEAT), and the Feller-Peterson-Dixon (FPD) approach enable sub-kJ/mol accuracy in gas-phase thermochemical properties. Their biggest computational bottleneck is the evaluation of the valence post-CCSD(T) correction term. We demonstrate here, for the W4-17 thermochemistry benchmark and subsets thereof, that the Λ coupled-cluster expansion converges more rapidly and smoothly than the regular coupled-cluster series. By means of CCSDT(Q)Λ and CCSDTQ(5)Λ, we can considerably (up to an order of magnitude) accelerate W4- and W4.3-type calculations without loss in accuracy, leading to the W4Λ and W4.3Λ computational thermochemistry protocols.Keywords
All Related Versions
Funding Information
- Israel Science Foundation (1969/20)
- Feinberg Graduate School, Weizmann Institute of Science
- Minerva Foundation (2020/05)
- Alexander S. Onassis Public Benefit Foundation (FZP 052-2/2021-2022)
This publication has 64 references indexed in Scilit:
- Electron Correlation: Nature's Weird and Wonderful Chemical GlueIsrael Journal of Chemistry, 2021
- Thermochemistry2019
- W4‐17: A diverse and high‐confidence dataset of atomization energies for benchmarking high‐level electronic structure methodsJournal of Computational Chemistry, 2017
- The Impact of Larger Basis Sets and Explicitly Correlated Coupled Cluster Theory on the Feller–Peterson–Dixon Composite Method2016
- A simple DFT-based diagnostic for nondynamical correlationTheoretical Chemistry Accounts, 2012
- A Practical Guide to Reliable First Principles Computational Thermochemistry Predictions Across the Periodic Table2012
- Gn theoryWIREs Computational Molecular Science, 2011
- W1 and W2 Theories, and Their Variants: Thermochemistry in the kJ/mol Accuracy Range2005
- Investigation of an asymmetric triple-excitation correction for coupled-cluster energiesInternational Journal of Quantum Chemistry, 1998
- A simple correction to final state energies of doublet radicals described by equation-of-motion coupled cluster theory in the singles and doubles approximationTheoretical Chemistry Accounts, 1996