Non-Born-Oppenheimer wavepacket dynamics in polyatomic molecules: vibrations at conical intersections in DABCO.

Non-adiabatic dynamics close to conical intersections and the surface hopping perspective

Conical intersections play a major role in the current understanding of electronic de-excitation in polyatomic molecules, and thus in the description of photochemistry and photophysics of molecular systems. This article reviews aspects of the basic theory underlying the description of non-adiabatic transitions at conical intersections, with particular emphasis on the important case when the dyn...

Non-Born–Oppenheimer Molecular Dynamics for Conical Intersections, Avoided Crossings, and Weak Interactions

Ultrafast 25-fs relaxation in highly excited states of methyl azide mediated by strong nonadiabatic coupling.

Highly excited electronic states are challenging to explore experimentally and theoretically-due to the large density of states and the fact that small structural changes lead to large changes in electronic character with associated strong nonadiabatic dynamics. They can play a key role in astrophysical and ionospheric chemistry, as well as the detonation chemistry of high-energy density materi...

Time-resolved photoelectron spectra of CS2: dynamics at conical intersections.

We report results of the application of a fully ab initio approach for simulating time-resolved molecular-frame photoelectron angular distributions around conical intersections in CS2. The technique employs wave packet densities obtained with the multiple spawning method in conjunction with geometry- and energy-dependent photoionization matrix elements. The robust agreement of these results wit...

Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems1–6. By contrast, time-resolved structural-dynamics methods such as electron7–10 or X-ray diffraction11 and X-ray absorption12 yield complementary information about t...