MRSF-TDDFT: A new tool in quantum chemistry for better understanding molecules and materials

Abstract

Quantum chemical theories are essential tools for predicting the properties of complex quantum systems without the need for prior empirical data. While traditional theories have long dominated the field, their applicability is often limited in complex scenarios, particularly for systems involving excited states. Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) addresses these challenges, offering a robust, accurate, and computationally efficient framework for studying both ground and excited states of large molecular systems. MRSF-TDDFT achieves predictive accuracy on par with much more computationally intensive quantum chemical methods. Notably, it successfully describes the doubly excited states, a limitation of conventional TDDFT, by naturally incorporating key doubly excited configurations within its response space. This capability also enables MRSF-TDDFT to accurately reproduce the correct asymptotic behavior of bond-breaking potential energy surfaces. Furthermore, it resolves critical photochemical features, such as the conical intersections, which elude both TDDFT and Complete Active Space Self-Consistent Field (CASSCF) methods. Despite its advanced predictive power, MRSF-TDDFT retains computational efficiency comparable to traditional TDDFT. With the development of custom-tailored functionals, its accuracy can be further enhanced, extending its potential applications. This innovation represents a significant advancement, empowering researchers to uncover intricate molecular behaviors and facilitate the design of novel materials with unprecedented precision.