Non-adiabatic molecular dynamics of molecules in the presence of strong light-matter interactions

Abstract

When confined photonic modes in an optical or plasmonic cavity interact strongly with a molecule, new hybrid light-matter states, termed as polaritonic states, can form. The newly formed polaritonic states are the superpositions of electrons (excitons) of the molecules and the cavity photonic modes. It was reported that these polaritons can be employed to control photochemical reactions, charge and energy transfer, and other processes. In addition, according to recent studies, vibrational strong coupling can be employed to resonantly enhance the thermally-activated chemical reactions. In this work, a theoretical model and an efficient numerical method for studying the dynamics of molecules strongly interacting with quantum light are developed based on non-adiabatic excited-state molecular dynamics. The methodology was employed to study the cis-trans photoisomerization of a realistic molecule in a cavity. Numerical simulations demonstrate that the photochemical reactions can be controlled by tuning the properties of the cavity. In the calculated example, the isomerization is suppressed when polaritonic states develop a local minimum on the lower polaritonic state. Moreover, the observed reduction of isomerization is tunable via the photon energy and lightmolecule coupling strength. These insights suggest quantum control of photochemical reactions is possible by specially designed photonic or plasmonic cavities. arXiv:1906.11210v1 [cond-mat.mes-hall]

Photochemistry in the strong coupling regime: A trajectory surface hopping scheme

“…In recent works, [24,34] we showed how the Surface Hopping scheme in a semiempirical framework can be used to describe the photochemistry of molecules in a strong coupling environment with a high level of realism. A similar Surface Hopping scheme has been used by Tretiak et al, [40] which studied the stilbene photoisomerization under strong coupling, employing a single reference quantum chemical approach for the electronic states. Comparatively, in our scheme, we also include cavity losses, and our semiempirical multireference FOMO-CI scheme allows for a qualitatively correct description of potential energy surfaces and couplings, which is also quantitatively accurate since we reparametrize the semiempirical Hamiltonian.…”

A formally exact one-frequency-only Bethe-Salpeter-like equation. Similarities and differences between GW +BSE and self-consistent RPA

“…In our scheme we obtain the same (approximate) dynamic contributions to the kernel as obtained by Sangalli et al [21] [see their Eqs. (22) and (23)]. They also contain the self-energy contributions.…”

“…A tentative list might include effects associated to double excitations in quantum chemistry [18] or to electron-hole screened interaction in metals [19]. Efforts to study dynamical BSE effects and introduce a real frequency dependence into the BSE have recently been attempted [20][21][22][23]. The standard BSE is an equation over two-body Green/correlation functions (kernel and response functions), i.e.…”

“…Recent efforts [20,21] have tried to redefine a kernel which incorporates frequency integration, to finally arrive at a more easily solvable one-frequency equation. Another approach [22,23] has considered the coupling of the linear-response function to uncorrelated two-particle-two-hole (2p-2h) states. The coupling of the linear-response function to collective states plus free particle-hole (p-h) states to account for double excitations has been discussed in Ref.…”

Dynamical configuration interaction: Quantum embedding that combines wave functions and Green's functions

“…14 There is not yet a widely adopted route to improve these shortcomings of the BSE, though developing extensions to both GW and BSE is a very active area of research. 13,[15][16][17][18][19][20][21][22][23][24][25][26][27][28] Dynamical mean-field theory (DMFT) is a quantum embedding theory based on the electronic GF. In combination with the local density approximation (LDA), LDA+DMFT [29][30][31] has been very successful in predicting spectral properties of strongly-correlated solids.…”