Approaching closed-shell accuracy for radicals using coupled cluster theory with perturbative triple substitutions

Literature Information

Publication Date 2003-05-09
DOI 10.1039/B304542K
Impact Factor 3.676
Authors

Gregory J. O. Beran, Steven R. Gwaltney, Martin Head-Gordon


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Abstract

The erratic performance of CCSD(T) for radicals is analyzed using non-Hartree–Fock references as a starting point for correlations and by testing the (2) approach as an alternative to (T) for including higher-order correlation effects. Though CCSD(2) improves upon CCSD(T), correlating from a better-behaved reference makes both theories robust. Comparisons of calculated harmonic frequencies against experiment in a set of diatomic radicals from Brueckner-like orbitals demonstrate improvement approaching closed-shell accuracy. Additionally, we find that using BLYP Kohn–Sham orbitals yields similar improvements, and they are therefore a useful, inexpensive reference for high-level correlation methods in difficult systems. Root-mean-square errors of 1.0–1.2% are found in the cc-pVQZ basis for predicted harmonic frequencies in the test set using OD(T) and KS-CCSD(T), making these approaches quite competitive with CCSD(T) for closed-shell molecules. Finally, these improvements are correlated with spin contamination and the rate of change of the electron density with nuclear displacement.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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