Deciphering Methylation Effects on S₂(ππ*) Internal Conversion in the Simplest Linear α,β-Unsaturated Carbonyl.

ABSTRACT: Chemical substituents can influence photodynamics by altering the location of critical points and the topography of the potential energy surfaces (electronic effect) and by selectively modifying the inertia of specific nuclear modes (inertial effects). Using nonadiabatic dynamics simulations, we investigate the impact of methylation on S₂(ππ*) internal conversion in acrolein, the simplest linear α,β-unsaturated carbonyl. Consistent with time constants reported in a previous time-resolved photoelectron spectroscopy study, S₂ → S₁ deactivation occurs on an ultrafast time scale (∼50 fs). However, our simulations do not corroborate the sequential decay model used to fit the experiment. Instead, upon reaching the S₁ state, the wavepacket bifurc

SUBMITTER: Chakraborty P 

PROVIDER: S-EPMC10316407 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature