Investigation of geometric phase effects in photodissociation dynamics at a conical intersection

Geometric phase effects in the ultracold D + HD $ \rightarrow $ D + HD and D + HD $\leftrightarrow $ H + D2reactions

“…In addition, excellent agreement was reported between the theoretically computed integral and DCSs computed without the GP and high resolution crossed molecular beam experiments [52,54,55]. The cancellation of the GP effect with respect to the partial wave sum was confirmed by Althorpe and co-workers using an entirely different computational methodology [56][57][58][59][60]. At higher scattering energies but below the energy of the conical intersection, Althorpe and coworkers found small oscillations in the DCSs due to the GP [56,61,62].…”

When do we need to account for the geometric phase in excited state dynamics?

“…To confirm these ideas through numerical simulations we plan to apply the developed analysis to non-LVC models of CIs in pyrrole. 28,29 Finally, in view of the DBOC compensating role of the GP it is clear why common approximations omitting the DBOC and GP contributions work quite well together in mixed quantum-classical non-adiabatic dynamics simulations. In addition, for non-adiabatic dynamics near the CI, adding the DBOC term should be accompanied by including the GP.…”

Interplay of electron-phonon nonadiabaticity and Raman scattering in the wavepacket dynamics of electron-phonon-photon systems

“…where (2) shows that the adiabatic PESs have a CI given by u = −ε/ν ′ and n i µ ′ i v i = −λ, and thus the geometrical phase of the wavefunction plays an important role on the dynamical properties 15 .…”

“…Furthermore, when electrons, phonons, and photons are considered at the same time, the Raman processes are expected to give significant contribution to the electronic transitions, which means that the photoexcitation/deexcitation process of electron-phonon systems should be carefully dealt with in order to understand the ultrafast dynamics with lightmatter interaction. As well as the intermodal coherence mediated by the Raman processes 12 , we stress that it is worth while mentioning that previous studies [13][14][15][16] have shown that the conical intersection(CI) in the "classical" adiabatic PESs also is a key to understand the wavepacket dynamics. These results show us that the coexistence of nonadiabatic coupling between PESs and Raman scattering processes gives another viewpoint on the coherent dynamics of electron-phonon-photon systems.…”