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.

Direct Signatures of Light-Induced Conical Intersections on the Field-Dressed Spectrum of Na2

“…Numerous theoretical and experimental studies have confirmed that LICIs have noticeable impact on different dynamical properties (like molecular alignment, photodissociation probability, etc...). [14][15][16][17][18][19] Furthermore, a strong effect in the angular distribution of the photofragments has been revealed that serves as a direct signature of the LICI. 18 The first experimental observation of LICIs in diatomic molecules was made by Bucksbaum et al.…”

Striking Generic Impact of Light-Induced Non-Adiabaticity in Polyatomic Molecules

“…give rise to a variety of unexpected nonadiabatic phenomena in molecules, [30][31][32][33][34] with significant impact on various dynamical [35][36][37][38] and spectroscopic properties. [39][40][41][42] These works were mainly focused on diatomic molecules where the angle between the internuclear axis and the field polarization axis provides the missing degree of freedom for a CI to emerge between two crossing field-dressed PESs.…”

Polariton Induced Conical Intersection and Berry Phase

“…Thus, it is vital to reveal the characteristic features of these LI-CIs. Previous theoretical studies, employing the classical description of light, investigated the nature of the LICI in diatomic molecules 32,33,[35][36][37][38][39][40] and to what extent the geometric phase of the LICI is similar to the natural CIs for polyatomic molecule in a field free space. 31,[41][42][43] It has been demonstrated that LICI strongly impact the spectroscopic and dynamical properties of molecules, such as the molecular alignment, the photodissociation probability, molecular spectra, and the angular distribution of the dissociation photofragment.…”