Restricted active space spin-flip configuration interaction approach: theory, implementation and examples

Literature Information

Publication Date 2009-08-18
DOI 10.1039/B911513G
Impact Factor 3.676
Authors

David Casanova, Martin Head-Gordon


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Abstract

A new formulation of the spin-flip (SF) method is presented. The electronic wave function is specified by the definition of an active space and through α-to-β excitations from a Hartree–Fock reference. The method belongs to the restricted active space (RAS) family, where the CI expansion is restricted by classifying the molecular orbitals in three subspaces. Properties such as spin completeness, variationality, size consistency, size intensivity, and orbital invariance are discussed. The implementation and applications use a particular truncation of the wave function, with the inclusion of hole and particle contributions such that for fixed active space size, the number of amplitudes is linear in molecular size. This approach is used to investigate single and double bond-breaking, the singlet–triplet gap of linear acenes, electronic transitions in three Ni(II) octahedral complexes, the low-lying states of the 2,5-didehydrometaxylylene (DDMX) tetraradical and the ground state multiplicity of 28 non-Kekulé structures. The results suggest that this approach can provide a quite well balanced description of nearly degenerate electronic states at moderate computational cost.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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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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