Surface hopping modeling of charge and energy transfer in active environments

Abstract

An active environment is any atomic or molecular system changing a chromophore's nonadiabatic dynamics compared to the isolated molecule. The action of the environment on the chromophore occurs by changing...

First-Principles Calculations of Excited-State Decay Rate Constants in Organic Fluorophores

“…When looking for high-accuracy approaches for describing competitive ES processes, NAMD and in particular the popular surface hopping (SH) approaches ,,, naturally come to mind. Unsurprisingly, such a dynamical strategy was sometimes applied to estimate the emission efficiency, and we briefly describe a few selected examples below.…”

LVC/MM: A Hybrid Linear Vibronic Coupling/Molecular Mechanics Model with Distributed Multipole-Based Electrostatic Embedding for Highly Efficient Surface Hopping Dynamics in Solution

“…7 These phenomena not only occur in isolated molecules in the gas phase but are also important in solution or even aggregated molecular systems� which could be subsumed as "complex systems". 13 Although TSH simulations (and other nonadiabatic dynamics techniques) can in principle elucidate essential details of the photoinduced process of molecular systems, they come at a sizable computational cost, especially for large systems. This cost arises because at every time step in TSH simulations, one needs to carry out excited-state electronic structure calculations, which yield the electronic potential energies, gradients, and nonadiabatic couplings.…”

“…Using TSH, it is possible to simulate fundamental processes such as internal conversion (IC) or intersystem crossing (ISC). − Therefore, TSH enables investigations into natural phenomena such as photoisomerization, photodissociation, and photocatalysis . These phenomena not only occur in isolated molecules in the gas phase but are also important in solution or even aggregated molecular systemswhich could be subsumed as “complex systems” …”

Different flavors of exact-factorization-based mixed quantum-classical methods for multistate dynamics

“…Still, these methods have led to useful results in many situations, where the use of more sophisticated schemes is not feasible. 10,22,23 Recently these methods have been extended to the polaritonic regime, where the coupled electron-ion-photon dynamics of systems of thousands of molecules confined to an optical cavity can be described running nuclear trajectories on the hybrid photonelectronic (polaritonic) surfaces. 24,25 An alternative view of nonadiabatic processes can be achieved through the exact factorization (EF) approach.…”