Electron and nuclear dynamics following molecular ionisation: computational methods and applications

The emergence of attosecond techniques has opened up the possibility to experimentally probe changes in the electron distribution, that until now have been treated as instantaneous. Photoionisation of molecules with attosecond (broad bandwidth) pulses leads to a non-stationary electronic wave packet. The current state-of-the-art for ab initio theory treats molecular electron dynamics as a purely electronic process, at a single fixed nuclear geometry. The present thesis is concerned with fundamental questions about the physics of non-stationary electronic wave packets and the coupling of this motion to that of the nuclei. To simulate coupled electron and nuclear dynamics, we use the “on-the-fly” mixed quantum-classical Ehrenfest method and the quantum mechanical DD-vMCG method. The results obtained with the two methods are compared. We choose to study electron and nuclear dynamics upon ionisation of benzene, toluene and para- xylene as examples because vertical ionisation takes place at geometries near the conical intersections between ground and first excited states of their cations, leading to a potentially strong coupling between the electronic and nuclear coordinates. One aim is to investigate electron dynamics and how it is affected by the nuclei. We show significant effects of the nuclear motion after a few femtoseconds within the Ehrenfest approximation. We also show how the inherent spatial delocalisation of the nuclei leads to very fast dephasing of electron dynamics, using a Wigner distribution. The DD-vMCG simulations confirm the very fast dephasing of electron dynamics in the molecules studied. A complementary aspect of the dynamics upon ionisation is the nuclear motion induced by an electronic wave packet. We show how the averaged initial nuclear motion (direction and velocity) is controlled by the composition of the electronic wave packet, as predicted by the Ehrenfest method. The DD-vMCG method provides the details of the nuclear dynamics on each electronic state.Open Acces

Dynamical Insights into the Decomposition of 1,2-Dioxetane

Chemiluminescence in 1,2-dioxetane occurs through a thermally activated decomposition reaction into two formaldehyde molecules. Both ground-state and nonadiabatic dynamics (including singlet excited states) of the decomposition reaction have been simulated, starting from the first O-O bond-breaking transition structure. The ground-state dissociation occurs between t = 30 fs and t = 140 fs. The so-called entropic trap leads to frustrated dissociations, postponing the decomposition reaction. Specific geometrical conditions are necessary for the trajectories to escape from the entropic trap and for dissociation to be possible. The singlet excited states participate as well in the trapping of the molecule: dissociation including the nonadiabatic transitions to singlet excited states now occurs from t = 30 fs to t = 250 fs and later. Specific regions of the seam of the S0/S1 conical intersections that would "retain" the molecule for longer on the excited state have been identified

How Do Methyl Groups Enhance the Triplet Chemiexcitation Yield of Dioxetane?

Chemiluminescence is the emission of light as a result of a nonadiabatic chemical reaction. The present work is concerned with understanding the yield of chemiluminescence, in particular how it dramatically increases upon methylation of 1,2-dioxetane. Both ground-state and nonadiabatic dynamics (including singlet excited states) of the decomposition reaction of various methyl-substituted dioxetanes have been simulated. Methyl-substitution leads to a significant increase in the dissociation time scale. The rotation around the O-C-C-O dihedral angle is slowed; thus, the molecular system stays longer in the "entropic trap" region. A simple kinetic model is proposed to explain how this leads to a higher chemiluminescence yield. These results have important implications for the design of efficient chemiluminescent systems in medical, environmental, and industrial applications

Photoionization time delays

International audienceThe material presented in this chapter is based on important advances realized in " attophysics " which make feasible to follow the motion of electrons in atoms and molecules with attosecond-level time resolution. In this context, time-delays have been recently determined in the process of photoionization by extreme-ultraviolet (xuv) pulses and the question of the significance of these measured delays arises. As we shall outline here, numerical experiments show that they are intimately related to the structure of the ionized species' continuous spectrum. Another point addressed here is that, in experiments, the measurements have the common characteristic to be performed in the presence of an auxiliary infra-red (IR) field, used to " clock " the timing of the process. This implies to adapt the theory treatment to handle such " two-color " photoionization processes. We review a systematic analysis of these features that are characteristic of this class of electronic transitions, when viewed in the time domain

Electron and nuclear dynamics following ionisation of modified bismethylene-adamantane

We have simulated the coupled electron and nuclear dynamics using the Ehrenfest method upon valence ionisation of modified bismethylene-adamantane (BMA) molecules where there is an electron transfer between the two π bonds. We have shown that the nuclear motion significantly affects the electron dynamics after a few fs when the electronic states involved are close in energy. We have also demonstrated how the non-stationary electronic wave packet determines the nuclear motion, more precisely the asymmetric stretching of the two π bonds, illustrating “charge-directed reactivity”. Taking into account the nuclear wave packet width results in the dephasing of electron dynamics with a half-life of 8 fs; this eventually leads to the equal delocalisation of the hole density over the two methylene groups and thus symmetric bond lengths

Male-induced early puberty correlates with the maturation of arcuate nucleus kisspeptin neurons in does

In goats, early exposure of spring-born females to sexually active bucks induces an early puberty onset assessed by the first ovulation. This effect is found when females are continuously exposed well before the male breeding season starting in September. The first aim of this study was to evaluate whether a shortened exposure of females to males could also lead to early puberty. We assessed the onset of puberty in Alpine does isolated from bucks (ISOL), exposed to wethers (CAS), exposed to intact bucks from the end of June (INT1), or mid-August (INT2). Intact bucks became sexually active in mid-September. At the beginning of October, 100% of INT1 and 90% of INT2 exposed does ovulated, in contrast to the ISOL (0%) and CAS (20%) groups. This demonstrated that contact with males that become sexually active is the main factor prompting precocious puberty in females. Furthermore, a reduced male exposure during a short window before the breeding season is sufficient to induce this phenomenon. The second aim was to investigate the neuroendocrine changes induced by male exposure. We found a significant increase in kisspeptin immunoreactivity (fiber density and number of cell bodies) in the caudal part of the arcuate nucleus of INT1 and INT2 exposed females. Thus, our results suggest that sensory stimuli from sexually active bucks (e.g., chemosignals) may trigger an early maturation of the ARC kisspeptin neuronal network leading to gonadotropin-releasing hormone secretion and first ovulation