Electron nuclear dynamics final-state analysis

Density functional theory, direct molecular dynamics, complete active space self-consistent field (CASSCF) technique, non-adiabatic systems, 404-411 Density operator, direct molecular dynamics, adiabatic systems, 375-377 Derivative couplings conical intersections, 569-570 direct molecular dynamics, vibronic coupling, conical intersections, 386-389 Determinantal wave function, electron nuclear dynamics (END), molecular systems, final-state analysis, 342-349 Diabatic representation ... 

Wigner rotation/adiabatic-to-diabatic transformation matrices, 92 Electronic structure theory, electron nuclear dynamics (END) structure and properties, 326-327 theoretical background, 324-325 time-dependent variational principle (TDVP), general nuclear dynamics, 334-337 Electronic wave function, permutational symmetry, 680-682 Electron nuclear dynamics (END) degenerate states chemistry, xii-xiii direct molecular dynamics, structure and properties, 327 molecular systems, 337-351 final-state analysis, 342-349 intramolecular electron transfer,... 

Reactive collisions, electron nuclear dynamics (END), molecular systems, 338—342 final-state analysis, 343 -349... 

Because the mapping approach treats electronic and nuclear dynamics on the same dynamical footing, its classical limit can be employed to study the phase-space properties of a nonadiabatic system. With this end in mind, we adopt a onemode two-state spin-boson system (Model IVa), which is mapped on a classical system with two degrees of freedom (DoF). Studying various Poincare surfaces of section, a detailed phase-space analysis of the problem is given, showing that the model exhibits mixed classical dynamics [123]. Furthermore, a number of periodic orbits (i.e., solutions of the classical equation of motion that return to their initial conditions) of the nonadiabatic system are identified and discussed [125]. It is shown that these vibronic periodic orbits can be used to analyze the nonadiabatic quantum dynamics [126]. Finally, a three-mode model of nonadiabatic photoisomerization (Model III) is employed to demonstrate the applicability of the concept of vibronic periodic orbits to multidimensional dynamics [127]. 

To our knowledge [63], there is no way to precisely control the temperature with the current experimental (e, 2e) setup which Liu et al. [45] used at Tsinghua University (Beijing, China) for their experiments on W(CO)g, a set-up which employs effusive molecular beams. In contrast with experiments based on free expansions in supersonic jets, it is usually assumed that the relatively high pressure in the collision cell ensures a full randomization of molecular motions, and thermal equilibrium therefore with the environment (298 K). Therefore, we wish to consider both the estimated experimental and standard room temperatures in our BOMD analysis. At last, the role played by nuclear dynamics in the final ionized state is also tentatively investigated. In this purpose, we revise before aU (theory section) how electron momentum distributions may vary in response to a change in the molecular geometry induced by ionization. 

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