title: Self-Consistent Constricted Variational Theory RSCF-CV(∞)-DFT and Its Restrictions To Obtain a Numerically Stable ΔSCF-DFT-like Method: Theory and Calculations for Triplet States.
abstract: In this paper, the relaxed self-consistent field infinite order constricted variational density functional theory (RSCF-CV(∞)-DFT) for triplet calculations is presented. Here, we focus on two main features of our implementation. First, as an extension of our previous work by Krykunov and Ziegler ( J. Chem. Theory Comput. 2013 , 9 , 2761 ), the optimization of the transition matrix representing the orbital transition is implemented and applied for vertical triplet excitations. Second, restricting the transition matrix, we introduce RSCF-CV(∞)-DFT-based numerically stable ΔSCF-DFT-like methods, the most general of them being SVD-RSCF-CV(∞)-DFT. The reliability of the different methods, RSCF-CV(∞)-DFT and its restricted versions, is examined using the benchmark test set of Silva-Junior et al. ( J. Chem. Phys. 2008 , 129 , 104103 ). The obtained excitation energies validate our approach and implementation for RSCF-CV(∞)-DFT and also show that SVD-RSCF-CV(∞)-DFT mimics very well ΔSCF-DFT, as the root-mean-square deviations between these methods are less than 0.1 eV for all functionals examined.
authors: Department of Chemistry, University of Calgary , 2500 University Drive Northwest, Calgary, Alberta T2N-1N4, Canada.
authors: Young Choon
authors: YC
authors: Park
authors: Department of Chemistry, University of Calgary , 2500 University Drive Northwest, Calgary, Alberta T2N-1N4, Canada.
authors: Florian
authors: F
authors: Senn
authors: Department of Chemistry and Biomolecular Sciences, University of Ottawa , 75 Laurier Avenue East, Ottawa, Ontario K1N-6N5, Canada.
authors: Mykhaylo
authors: M
authors: Krykunov
authors: Department of Chemistry, University of Calgary , 2500 University Drive Northwest, Calgary, Alberta T2N-1N4, Canada.
authors: Tom
authors: T
authors: Ziegler