Koopmans' multiconfigurational self-consistent field (MCSCF) Fukui functions and MCSCF perturbation theory

摘要

Prediction of chemical reactivity has become one of the highest priority tasks of computational chemistry since the development of the methods of modeling electronic structure. Despite the general simplicity of the physical concept of reactivity and the rapid development of modern density functional theory (DFT) methods, this task remains state-of-the-art for systems with wavefunctions that have a multiconfigurational character. In such cases, for the accurate description of reactivity one needs to use multiconfigurational approaches that are much heavier computationally then ordinary single-determinant DFT methods. Moreover, the complexity of the calculation of reactivity is increased by the necessity to calculate ionic and transition states. These computational challenges can be addressed by employing the concepts of Koopmans' theorem and its extension to a multiconfigurational case. We present a simplified methodology for the calculation of Fukui functions, based on Koopmans' approximation for multiconfigurational Green's functions developed in our previous works. Also, an extension of this methodology based on perturbation theory has been developed to improve accuracy.