SearcharxivSearch

arXiv · 1607.02300

Towards controlling the dissociation probability by light-induced conical intersections

Abstract

Light-induced conical intersections (LICIs) can be formed both by standing or by running laser waves. The position of a LICI is determined by the laser frequency while the laser intensity controls the strength of the nonadiabatic coupling. Recently, it was shown within the LICI framework that linearly chirped laser pulses have an impact on the dissociation dynamics of the $D_{2}^{+}$ molecule (J. Chem. Phys. 143, 014305, (2015); ibid 144, 074309, (2016)). In this work we exploit this finding and perform calculations using chirped laser pulses in which the time dependence of the laser frequency is designed so as to force the LICI to move together with the field-free vibrational wave packet as much as possible. Since nonadiabaticity is strongest in the vicinity of the conical intersection, this is the first step towards controlling the dissociation process via the LICI. Our showcase example is again the $D_{2}^{+}$ molecular ion. To demonstrate the impact of the LICIs on the dynamical properties of diatomics, the total dissociation probabilities and the population of the different vibrational levels after the dissociation process are studied and discussed.

Explore related subjects

Keep this discovery

BibTeXRIS

András Csehi, Gábor J. Halász, Lorenz S. Cederbaum, Ágnes Vibók. 2016-07-08. Towards controlling the dissociation probability by light-induced conical intersections. https://doi.org/10.1039/c6fd00139d

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

Core-Level Spectroscopy Decodes Bond-Alternation Dynamics of Cyclo[18]Carbon

The advent of X-ray free-electron lasers and high-harmonic generation has made time-resolved X-ray spectroscopy a powerful tool for probing local atomic environments, yet whether localized core excitations can report on global collective distortions remains open. Cyclo[18]carbon (C$_{18}$), with its polyynic ground state (D$_\text{9h}$) and cumulenic transition state (D$_\text{18h}$), provides an ideal model to address this long-standing issue in bond-length alternation (BLA) dynamics. Mapping two-dimensional potential energy surfaces by first-principles simulations, we find that core ionization symmetrizes the ground-state double-well potential along the BLA coordinate. Our calculated X-ray spectra reveal remarkable sensitivity to bond-length variations: C1s ionization potentials vary by up to 2.4~eV across the BLA coordinate (1.1--1.4~\AA), with a 0.9~eV variation for minima predicted by different functionals, while NEXAFS $\pi^*$ peaks shift by up to 4~eV across the same coordinate. These predicted signatures provide a quantitative spectroscopy--structure dictionary for decoding transient structures in future ultrafast X-ray experiments and monitoring bond-alternation dynamics in real time.

physics.atm-clus

X-ray photoelectron spectroscopy of Ar and Kr clusters formed in He nanodroplets

We report the first soft x-ray photoelectron spectroscopy (XPS) measurements of Ar and Kr clusters formed inside superfluid helium nanodroplets (HNDs) through consecutive pickup of dopant atoms. Ar and Kr atoms and clusters are selectively inner-shell ionized (Ar 2p, Kr 3d) using monochromatic soft x-ray synchrotron radiation. In the regime of strong doping, the electron spectra exhibit features characteristic of free Ar and Kr atoms as well as their clusters. The Kr cluster spectra agree well with literature data for bare Kr clusters. Backed by detailed simulations of the pickup process, this agreement indicates that the observed spectra originate from nearly bare Ar and Kr clusters, from which most or all He has evaporated in the course of cluster aggregation. These results establish HNDs as a platform for XPS of various types of molecular complexes and nanostructures.

physics.atm-clus

What is superatom?

The term "superatom" was introduced over three decades ago to describe clusters that emulate elemental atoms. The field has long been guided by the spherical jellium model, where magic numbers arise from shell closure of delocalized electrons. This Perspective argues that delocalization, not near-sphericity, is what makes a system atom-like. It shows that superatomic shell structure persists under arbitrary point-group symmetry, that superatomicity survives as a tunable quantum state across pressurized, ionized, and chemically precompressed systems, and that the symmetry rules governing superatoms are conditional, deeper than the jellium picture admits. The future of this field lies not in finding more magic numbers, but in exploiting superatomic states as artificial quantum systems at the atomic level.

physics.atm-clus