Redesign of the DFT/MRCI Hamiltonian

• Published in: The Journal of chemical physics 2016-01, Vol.144 (3), p.034104-034104
• Main Authors: Lyskov, Igor, Kleinschmidt, Martin, Marian, Christel M.
• Format: Article
• Language: English
• Subjects: ALGORITHMS; Chromophores; COMPARATIVE EVALUATIONS; Computing time; CONFIGURATION INTERACTION; DAMPING; DENSITY FUNCTIONAL METHOD; Density functional theory; Dependence; EFFICIENCY; ELECTRON CORRELATION; Excimers; EXCITATION; EXCITED STATES; FUNCTIONS; Hamiltonian functions; HAMILTONIANS; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MATRIX ELEMENTS; MOLECULES; Organic chemistry; Parameterization; Physics; Quantum chemistry; Redesign; Robustness (mathematics); SPIN; STATISTICS; TRIPLETS; Upconversion; YIELDS
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4940036

The combined density functional theory and multireference configuration interaction (DFT/MRCI) method of Grimme and Waletzke [J. Chem. Phys. 111, 5645 (1999)] is a well-established semi-empirical quantum chemical method for efficiently computing excited-state properties of organic molecules. As it turns out, the method fails to treat bi-chromophores owing to the strong dependence of the parameters on the excitation class. In this work, we present an alternative form of correcting the matrix elements of a MRCI Hamiltonian which is built from a Kohn-Sham set of orbitals. It is based on the idea of constructing individual energy shifts for each of the state functions of a configuration. The new parameterization is spin-invariant and incorporates less empirism compared to the original formulation. By utilizing damping techniques together with an algorithm of selecting important configurations for treating static electron correlation, the high computational efficiency has been preserved. The robustness of the original and redesigned Hamiltonians has been tested on experimentally known vertical excitation energies of organic molecules yielding similar statistics for the two parameterizations. Besides that, our new formulation is free from artificially low-lying doubly excited states, producing qualitatively correct and consistent results for excimers. The way of modifying matrix elements of the MRCI Hamiltonian presented here shall be considered as default choice when investigating photophysical processes of bi-chromophoric systems such as singlet fission or triplet-triplet upconversion.