Ultrafast Internal Conversion in Ethylene I. The Excited State Lifetime

TL;DR

This study combines theoretical simulations and experimental data to accurately determine the excited state lifetime of ethylene, resolving a decade-long discrepancy between observed and predicted lifetimes.

Contribution

It introduces a detailed ab initio simulation approach that aligns well with experimental TRPES data, clarifying the mechanisms behind ethylene's excited state decay.

Findings

Excellent agreement between simulation and experiment.

Fast decay driven by energetic and electronic factors.

Resolves long-standing lifetime discrepancy.

Abstract

Using a combined theoretical and experimental approach, we investigate the non-adiabatic dynamics of the prototypical ethylene (C2H4) molecule upon {\pi} \to {\pi}* excitation. In this first part of a two part series, we focus on the lifetime of the excited electronic state. The femtosecond Time-Resolved Photoelectron Spectrum (TRPES) of ethylene is simulated based on our recent molecular dynamics simulation using the ab initio multiple spawning method (AIMS) with Multi-State Second Order Perturbation Theory (Tao, et al. J. Phys. Chem. A 113 13656 2009). We find excellent agreement between the TRPES calculation and the photoion signal observed in a pump-probe experiment using femtosecond vacuum ultraviolet (h{\nu} = 7.7 eV) pulses for both pump and probe. These results explain the apparent discrepancy over the excited state lifetime between theory and experiment that has existed for ten years, with experiments (e.g., Farmanara, et al. Chem. Phys. Lett. 288 518 1998 and Kosma, et al. J. Phys. Chem. A 112 7514 2008) reporting much shorter lifetimes than predicted by theory. Investigation of the TRPES indicates that the fast decay of the photoion yield originates from both energetic and electronic factors, with the energetic factor playing a larger role in shaping the signal.