Intersection conique

Résumé

thumb|Intersection conique idéale entre deux surfaces d'énergie potentielle. Les axes horizontaux représentent les positions nucléaires, l'axe vertical est l'énergie des deux états possibles. En chimie quantique, une intersection conique de deux surfaces d'énergie potentielle (SEP) de mêmes symétries spatiales et de spin est l'ensemble des points géométriques où deux SEP sont dégénérées (se croisent). Les intersections coniques se rencontrent dans tous les systèmes chimiques triviaux et non triviaux. Dans un système à deux coordonnées, ce phénomène peut se produire pour une géométrie donnée. Si les SEP sont tracées comme des fonctions des deux coordonnées, elles forment un cône centré sur le point de dégénérescence. Cela est montré sur la figure de droite, les SEP inférieure et supérieure ayant deux couleurs différentes. Le nom d'intersection conique provient de cette observation. De manière plus générale, on trouve des intersections coniques lorsque pour une même géométrie, il exist

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https://fr.wikipedia.org/wiki/Intersection_conique

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This course introduces modern computational electronic structure methods and their broad applications to organic chemistry. It also discusses physical organic concepts to illustrate the stability and reactivity of organic molecules.

Le cours comporte deux parties. Les bases de la thermodynamique des équilibres et de la cinétique des réactions sont introduites dans l'une d'elles. Les premières notions de chimie quantique sur les électrons et les liaisons chimiques, exemplifiées en chimie organique, sont présentées dans l'autre.

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High-order geometric integrators for nonadiabatic molecular quantum dynamics and their applications to explore conical intersections

Seonghoon Choi

Accurate simulations of molecular quantum dynamics are crucial for understanding numerous natural processes and experimental results. Yet, such high-accuracy simulations are challenging even for relatively simple systems where the Born-Oppenheimer approximation is valid. Worse still, due to the ubiquity of conical intersections in molecules, it is often necessary to go beyond this celebrated approximation and employ even more sophisticated methods that can describe nonadiabatic processes involving multiple coupled electronic states.Geometric integrators provide a way to simulate nonadiabatic quantum dynamics with high accuracy while exactly conserving geometric properties, such as norm, energy, symplecticity, and time reversibility. However, the exact conservation of these properties typically leads to a higher computational cost when compared with non-geometric integrators of the same order of accuracy. We remedy this lack of efficiency by employing various composition methods to obtain high-order geometric integrators, competitive in efficiency even with some non-geometric integrators.To overcome the limited applicability of the popular split-operator algorithms, we present geometric integrators that can solve the time-dependent Schroedinger equation efficiently regardless of the form of the Hamiltonian. Employing these integrators, we systematically compare the different representations of the molecular Hamiltonian for their suitability for simulating nonadiabatic dynamics at a conical intersection and find that the rarely used exact quasidiabatic Hamiltonian, which includes the often-neglected residual nonadiabatic couplings, yields the most accurate results. Accordingly, we present a method for quantifying the validity of ignoring these residual couplings and show that depending on the system, initial state, and employed quasidiabatization scheme, neglecting the residual couplings can indeed result in inaccurate dynamics.The computational cost of exact quantum simulations quickly becomes prohibitively high as the system size increases. For high-dimensional simulations, one can either optimize the available basis set, e.g., by employing adaptive phase space grids or, alternatively, employ a more approximate approach, such as mixed quantum-classical Ehrenfest dynamics, that provides a useful qualitative picture. Although Ehrenfest dynamics and exact quantum dynamics simulated on an adaptive grid may appear unrelated, we show that, surprisingly, the high-order geometric integrators for these two problems can, in fact, be obtained by using the same splitting and composition methods.

EPFL2022

Chargement

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We present a combined experimental and computational study of the relaxation dynamics of the ethylene cation. In the experiment, we apply an extreme-ultraviolet-pump/infrared-probe scheme that permits us to resolve time scales on the order of 10 fs. The photoionization of ethylene followed by an infrared (IR) probe pulse leads to a rich structure in the fragment ion yields reflecting the fast response of the molecule and its nuclei. The temporal resolution of our setup enables us to pinpoint an upper bound of the previously defined ethylene ethylidene isomerization time to 30 +/- 3 fs. Time dependent density functional based trajectory surface hopping simulations show that internal relaxation between the first excited states and the ground state occurs via three different conical intersections. This relaxation unfolds on femtosecond time scales and can be probed by ultrashort IR pulses. Through this probe mechanism, we demonstrate a route to optical control of the important dissociation pathways leading to separation of H or H-2.

2016

Chargement

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The mechanism of aggregation-induced emission, which overcomes the common aggregation-caused quenching problem in organic optoelectronics, is revealed by monitoring the real time structural evolution and dynamics of electronic excited state with frequency and polarization resolved ultrafast UV/IR spectroscopy and theoretical calculations. The formation of Woodward-Hoffmann cyclic intermediates upon ultraviolet excitation is observed in dilute solutions of tetraphenylethylene and its derivatives but not in their respective solid. The ultrafast cyclization provides an efficient nonradiative relaxation pathway through crossing a conical intersection. Without such a reaction mechanism, the electronic excitation is preserved in the molecular solids and the molecule fluoresces efficiently, aided by the very slow intermolecular charge and energy transfers due to the well separated molecular packing arrangement. The mechanisms can be general for tuning the properties of chromophores in different phases for various important applications.

WILEY-V C H VERLAG GMBH2020

Chargement

High-order geometric integrators for nonadiabatic molecular quantum dynamics and their applications to explore conical intersections

Seonghoon Choi

EPFL2022