Conical Intersections using Constrained DFT-Configuration Interaction
Author(s)Kaduk, Benjamin James; Van Voorhis, Troy
Communication: Conical intersections using constrained density theory-configuration interaction
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The constrained density functional theory–configuration interaction (CDFT-CI) method has previously been used to calculate ground-state energies and barrier heights. In this work, it is examined for use in computing electronic excited states, for the challenging case of conical intersections. Conical intersections are a prevalent feature of excited electronic surfaces, but conventional time-dependent density functional theory calculations are found to be entirely unsatisfactory at describing them, for two small systems. CDFT-CI calculations on those systems are found to be in qualitative agreement with reference CAS surfaces. These results suggest that with a suitable definition of atomic populations and a careful choice of constrained states, CDFT-CI could be the basis for a seamless description of electronic degeneracy.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
Journal of Chemical Physics
American Institute of Physics
Kaduk, Benjamin, and Troy Van Voorhis. “Communication: Conical Intersections Using Constrained Density Functional Theory–configuration Interaction.” The Journal of Chemical Physics 133.6 (2010): 061102. Web.
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