The DFT/MRCI method

Abstract

In the past two decades, the combined density functional theory and multireference configuration interaction (DFT/MRCI) method has developed from a powerful approach for computing spectral properties of singlet and triplet excited states of large molecules into a more general multireference method applicable to states of all spin multiplicities. In its original formulation, it shows great efficiency in the evaluation of singlet and triplet excited states which mainly originate from local one-electron transitions. Moreover, DFT/MRCI is one of the few methods applicable to large systems that yields the correct ordering of states in extended π-systems where double excitations play a significant role. A recently redesigned DFT/MRCI Hamiltonian extends the application range of the method to bi-chromophores such as hydrogen-bonded or π-stacked dimers and loosely coupled donor–acceptor systems. In conjunction with a restricted-open shell Kohn–Sham optimization of the molecular orbitals, even electronically excited doublet and quartet states can be addressed. After a short outline of the general ideas behind this semi-empirical method and a brief review of alternative approaches combining density functional and multireference wavefunction theory, formulae for the DFT/MRCI Hamiltonian matrix elements are presented and the adjustments of the two-electron contributions are discussed. The performance of the DFT/MRCI variants on excitation energies of organic molecules and transition metal compounds against experimental or ab initio reference data is analyzed and case studies are presented which show the strengths and limitations of the method. Finally, an overview over the properties available from DFT/MRCI wavefunctions and further developments is given. This article is categorized under: Electronic Structure Theory > Density Functional Theory Electronic Structure Theory > Semiempirical Electronic Structure Methods Software > Quantum Chemistry.