Spin-Flip Dynamics Beyond Standard Models: Real-Time Nonadiabatic Simulations in Complex Photophysical Systems

While Casanova & Krylov (2020) review static and some dynamical applications of spin-flip methods, the real-time evolution of spin-forbidden processes in complex systems is still largely unexplored. This research would integrate spin-flip methods into nonadiabatic molecular dynamics (building on techniques like those discussed by Spinlove 2018, and Xu et al. 2018), simulating ultrafast intersystem crossing and photorelaxation in challenging systems such as vanadium(III) complexes (Dorn et al. 2021) or organic emitters. This goes beyond current work by explicitly modeling how the spin-flip formalism handles strongly coupled electronic and nuclear dynamics, potentially revealing new mechanistic insights or limitations. The innovation is in bridging accurate, spin-adapted quantum chemistry with time-resolved simulations, providing a more realistic picture of excited-state dynamics and helping refine or challenge accepted models of photorelaxation.

References:

1. Spin-flip methods in quantum chemistry.. D. Casanova, A. Krylov (2020). Physical Chemistry, Chemical Physics - PCCP.
2. Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry. Matthias Dorn, Jens Kalmbach, P. Boden, Ayla Kruse, C. Dab, C. Reber, G. Niedner‐Schatteburg, S. Lochbrunner, M. Gerhards, Michael Seitz, K. Heinze (2021). Chemical Science.
3. Methods for the treatment of multiple states in non-adiabatic direct quantum dynamics simulations. K. E. Spinlove (2018).
4. An excited-state Wolff rearrangement reaction of 5-diazo Meldrum's acid: an ab initio on-the-fly nonadiabatic dynamics simulation.. Chao Xu, F. Gu, Chaoyuan Zhu (2018). Physical Chemistry, Chemical Physics - PCCP.