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1. Modeling Non-adiabatic Dynamics in Nanoscale and Condensed Matter Systems

   https://doi.org/10.1021/acs.accounts.1c00525  

   Prezhdo, Oleg V. (December 2021, Accounts of Chemical Research)
2. Non-adiabatic ring polymer molecular dynamics with spin mapping variables

   https://doi.org/10.1063/5.0051456  

   Bossion, Duncan; Chowdhury, Sutirtha N.; Huo, Pengfei (May 2021, The Journal of Chemical Physics)
3. Ab initio spin-mapping non-adiabatic dynamics simulations of photochemistry

   https://doi.org/10.1063/5.0248950  

   Weight, Braden M; Mandal, Arkajit; Hu, Deping; Huo, Pengfei (February 2025, The Journal of Chemical Physics)

   We perform on-the-fly non-adiabatic molecular dynamics simulations using the recently developed spin-mapping formalism. Two quantum dynamics approaches based on this mapping formalism, (i) the fully linearized Spin-LSC and (ii) the partially linearized Spin-PLDM, are explored using the quasi-diabatic propagation scheme. We have performed dynamics simulations in four ab initio molecular models for which benchmark ab initio multiple spawning (AIMS) data have been published. We find that the spin-LSC and the previously reported symmetric quasi-classical (SQC) approaches provide nearly equivalent population dynamics. While we expected the more involved spin-PLDM method to provide superior accuracy compared to the other mapping-based approaches, SQC and spin-LSC, we found that it performed with equivalent accuracy compared to the AIMS benchmark results. We further explore the underpinnings of the spin-PLDM correlation function by decomposing its N2 density matrix-focused initial conditions, where N is the number of states in the quantum subsystem. Finally, we found an approximate form of the spin-PLDM correlation function, which simplifies the simulation and reduces the computational costs from N2 to N. 

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4. Trajectory-based non-adiabatic simulations of the polariton relaxation dynamics

   https://doi.org/10.1063/5.0246099  

   Hu, Deping; Chng, Benjamin_X K; Ying, Wenxiang; Huo, Pengfei (March 2025, The Journal of Chemical Physics)

   We benchmark the accuracy of various trajectory-based non-adiabatic methods in simulating the polariton relaxation dynamics under the collective coupling regime. The Holstein–Tavis–Cummings Hamiltonian is used to describe the hybrid light–matter system of N molecules coupled to a single cavity mode. We apply various recently developed trajectory-based methods to simulate the population relaxation dynamics by initially exciting the upper polariton state and benchmark the results against populations computed from exact quantum dynamical propagation using the hierarchical equations of motion approach. In these benchmarks, we have systematically varied the number of molecules N, light–matter detunings, and the light–matter coupling strengths. Our results demonstrate that the symmetrical quasi-classical method with γ correction and spin-mapping linearized semi-classical approaches yield more accurate polariton population dynamics than traditional mixed quantum-classical methods, such as the Ehrenfest and surface hopping techniques. 

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5. Tracking ultrafast non-adiabatic dissociation dynamics of the deuterated water dication molecule

   https://doi.org/10.1063/5.0219029  

   Iskandar, W; Rescigno, T N; Orel, A E; Larsen, K A; Severt, T; Streeter, Z L; Jochim, B; Griffin, B; Call, D; Davis, V; et al (July 2024, The Journal of Chemical Physics)

   We applied reaction microscopy to elucidate fast non-adiabatic dissociation dynamics of deuterated water molecules after direct photo-double ionization at 61 eV with synchrotron radiation. For the very rare D+ + O+ + D breakup channel, the particle momenta, angular, and energy distributions of electrons and ions, measured in coincidence, reveal distinct electronic dication states and their dissociation pathways via spin–orbit coupling and charge transfer at crossings and seams on the potential energy surfaces. Notably, we could distinguish between direct and fast sequential dissociation scenarios. For the latter case, our measurements reveal the geometry and orientation of the deuterated water molecule with respect to the polarization vector that leads to this rare 3-body molecular breakup channel. Aided by multi-reference configuration-interaction calculations, the dissociation dynamics could be traced on the relevant potential energy surfaces and particularly their crossings and seams. This approach also unraveled the ultrafast time scales governing these processes. 

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