期刊
JOURNAL OF CHEMICAL PHYSICS
卷 143, 期 23, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4937571
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资金
- National Science Foundation [CHE-1300603]
- Ohio Supercomputer Center [PAA-0003]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1300603] Funding Source: National Science Foundation
We revisit the formalism of the spin-adapted, spin-flip (SA-SF) configuration-interaction singles (CIS) method based on a tensor equation-of-motion formalism that affords proper spin eigenstates without sacrificing single-reference simplicity. Matrix elements for SA-SF-CIS are then modified in a manner similar to collinear spin-flip time-dependent density functional theory (SF-TDDFT), to include a DFT exchange-correlation correction. The performance of this method, which we call SA-SF-DFT, is evaluated numerically and we find that it systematically improves the energies of electronic states that exhibit significant spin contamination within the conventional SF-TDDFT approach. The new method cures the state assignment problem that plagues geometry optimizations and ab initio molecular dynamics simulations using traditional SF-TDDFT, without sacrificing computational efficiency, and furthermore provides correct topology at conical intersections, including those that involve the ground state, unlike conventional TDDFT. As such, SA-SF-DFT appears to be a promising method for generating excited-state potential energy surfaces at DFT cost. (C) 2015 AIP Publishing LLC.
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