Fragmentation of long-lived hydrocarbons after strong field ionization

TL;DR

This study combines experimental and theoretical methods to analyze the delayed deprotonation of hydrocarbons after strong field ionization, revealing vibrational tunneling as a key mechanism independent of laser parameters.

Contribution

It provides new insights into the long-lived dication states and their fragmentation pathways, highlighting vibrational tunneling as a primary process.

Findings

Delayed deprotonation is unaffected by laser pulse duration and intensity.

Vibrational tunneling causes delayed fragmentation in hydrocarbons.

Different excitation pathways lead to vibrational states involved in fragmentation.

Abstract

We experimentally and theoretically investigated the deprotonation process on nanosecond to microsecond timescale in ethylene and acetylene molecules, following their double ionization by a strong femtosecond laser field. In our experiments we utilized coincidence detection with the reaction microscope technique, and found that both the lifetime of the long-lived ethylene dication leading to the delayed deprotonation and the relative channel strength of the delayed deprotonation compared to the prompt one have no evident dependence on the laser pulse duration and the laser peak intensity. Quantum chemical simulations suggest that such delayed fragmentation originates from the tunneling of near-dissociation-threshold vibrational states through a dissociation barrier on a dication electronic state along C--H stretching. Such vibrational states can be populated through strong field double ionization induced vibrational excitation on an electronically excited state in the case of ethylene, and through intersystem crossing from electronically excited states to the electronic ground state in the case of acetylene.