Work

A spin-complete version of the spin-flip approach to bond breaking: What is the impact of obtaining spin eigenfunctions?

Year: 2003

Type: article

Abstract: Spin-complete versions of the spin-flip configuration-interaction-singles (SF-CIS) approach have been investigated to determine the impact of making the wave function an eigenfunction of Ŝ2. The method has been implemented within an extended restricted active space configuration interaction formalism. Spin-complete results are presented for excitation energies, equilibrium geometries, and potential energy curves for dissociation of a single bond in several small molecules. The effect of different orbital choices has also been investigated. The spin-complete results are compared both to results using the original spin-flip method and to more computationally expensive benchmarks. Using spin eigenfunctions dramatically improves upon the accuracy of the SF-CIS approach.

Source: The Journal of Chemical Physics

DOI: 10.1063/1.1568735

Authors: John S. Sears, C. David Sherrill, Anna I. Krylov

Institutions: Georgia Institute of Technology, University of Southern California

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: bronze

Funders: National Science Foundation, American Chemical Society Petroleum Research Fund, Division of Chemistry

Awards: CAREER: Theoretical Studies of Bond-Breaking, Diradicals, and Nondynamical Correlation, G5986892838, G6671297155, CAREER: Ab Initio Modeling of Radiationless Processes: Excited States of Open-Shell Species and Spin-Forbidden Reactions