Roaming in acetaldehyde

TL;DR

This study explores the roaming mechanisms in acetaldehyde photodissociation, revealing two distinct pathways with different dynamics, and suggests that multiple roaming routes contribute to its increased propensity compared to formaldehyde.

Contribution

It identifies and characterizes two separate roaming pathways in acetaldehyde, including a unique short-range mechanism facilitated by repulsive interactions, expanding understanding of molecular roaming dynamics.

Findings

Two distinct roaming pathways identified with different separations.

Short-range roaming is unique to acetaldehyde and involves repulsive interactions.

Multiple roaming mechanisms explain increased roaming propensity in acetaldehyde.

Abstract

We investigate roaming in the photodissociation of acetaldehyde (CH$_3$CHO), providing insight into the contrasting roaming dynamics observed for this molecule compared to formaldehyde. We carry out trajectory studies for full-dimensional acetaldehyde, supplemented with an analysis of a two degree-of-freedom restricted model and obtain evidence for two distinct roaming pathways. Trajectories exhibit roaming at both shorter (9-11.5 au) and larger (14.5-22.9 au) maximum CH$_3$-HCO separations, characterized by differing amounts of HCO rotation. No roaming trajectories were found in the intervening gap region. The roaming dynamics near 14.5-22.9 au are well-reproduced by the restricted model and involve passage through a centrifugal barrier, analogous to formaldehyde roaming. However, the shorter-range 9-11.5 au roaming appears unique to acetaldehyde, and is likely facilitated by repulsive interactions absent in the simplified models. Phase space analysis reveals that this additional roaming pathway is inaccessible in the reduced dimensionality system. The findings suggest acetaldehyde's increased propensity for roaming compared to formaldehyde may arise from the presence of multiple distinct roaming mechanisms rather than solely the higher roaming fragment mass.