The effect of local approximations in coupled-cluster wave functions on dipole moments and static dipole polarisabilities

Literature Information

Publication Date 2004-03-31
DOI 10.1039/B316709G
Impact Factor 3.676
Authors

Klaus Pflüger, Hans-Joachim Werner


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Abstract

The influence of local approximations in electron correlation treatments on electric dipole moments and static dipole polarisabilities is examined for a test set of 16 molecules for the case of coupled-cluster singles and doubles (CCSD) theory. Utilising standard local approximations as originally proposed by Pulay and used in our previous work, the average errors relative to the corresponding conventional CCSD calculations amount to 0.48% for mean dipole polarisabilities and to 1.61% for dipole moments. The accuracy of the computed mean dipole polarisabilities can be reduced to 0.32% by extending the domains of the strong pairs, while for the dipole moments the domain extension reduces the error to 0.91%. It is found that orbital relaxation effects are much more important in the local than in the conventional case. Weak pairs contribute substantially to the computed dipole polarisabilities, but the effect of distant pairs is small and can be neglected. This means that linear scaling local electron correlation methods can be faithfully used to compute these molecular properties.

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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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