Search Results
Sub-laser-cycle control of coupled electron–nuclear dynamics at a conical intersection
2015, Richter, Maria, Bouakline, Foudhil, González-Vázquez, Jesús, Martínez-Fernández, Lara, Corral, Inés, Patchkovskii, Serguei, Morales, Felipe, Ivanov, Misha, Martín, Fernando, Smirnova, Olga
Nonadiabatic processes play a fundamental role in the understanding of photochemical processes in excited polyatomic molecules. A particularly important example is that of radiationless electronic relaxation at conical intersections (CIs). We discuss new opportunities for controlling coupled electron–nuclear dynamics at CIs, offered by the advent of nearly single-cycle, phase-stable, mid-infrared laser pulses. To illustrate the control mechanism, a two-dimensional model of the NO2 molecule is considered. The key idea of the control scheme is to match the time scale of the laser field oscillations to the characteristic time scale of the wave packet transit through the CI. The instantaneous laser field changes the shape and position of the CI as the wave packet passes through. As the CI moves in the laser field, it 'slices' through the wave packet, sculpting it in the coordinate and momentum space in a way that is sensitive to the carrier-envelope phase of the control pulse. We find that the electronic coherence imparted on the sub-laser-cycle time scale manifests during much longer nuclear dynamics that follow on the many tens of femtosecond time scale. Control efficiency as a function of molecular orientation is analyzed, showing that modest alignment is sufficient for showing the described effects.
Signatures of attosecond electronic–nuclear dynamics in the one-photon ionization of molecular hydrogen: analytical model versusab initiocalculations
2015, Medišauskas, Lukas, Morales, Felipe, Palacios, Alicia, González-Castrillo, Alberto, Plimak, Lev, Smirnova, Olga, Martín, Fernando, Ivanov, Misha Yu
We present an analytical model based on the time-dependent WKB approximation to reproduce the photoionization spectra of an H2 molecule in the autoionization region. We explore the nondissociative channel, which is the major contribution after one-photon absorption, and we focus on the features arising in the energy differential spectra due to the interference between the direct and the autoionization pathways. These features depend on both the timescale of the electronic decay of the autoionizing state and the time evolution of the vibrational wavepacket created in this state. With full ab initio calculations and with a one-dimensional approach that only takes into account the nuclear wavepacket associated to the few relevant electronic states we compare the ground state, the autoionizing state, and the background continuum electronic states. Finally, we illustrate how these features transform from molecular-like to atomic-like by increasing the mass of the system, thus making the electronic decay time shorter than the nuclear wavepacket motion associated with the resonant state. In other words, autoionization then occurs faster than the molecular dissociation into neutrals.