Photo-induced electronic excitations drive polymerization of carbon monoxide: A first-principles study

TL;DR

This study uses first-principles simulations to show that laser-induced electronic excitations can promote polymerization of CO at lower pressures, offering a new photo-assisted synthesis route for energetic materials.

Contribution

It demonstrates how electronic excitation enhances C-C bonding in CO, enabling polymerization at reduced pressures through a first-principles computational approach.

Findings

Electronic excitation facilitates CO polymerization at lower pressures.

Laser irradiation can induce polymerization without high pressure.

The resulting polymeric phase is metastable and energy-releasing.

Abstract

Under pressure, carbon monoxide (CO) transforms into a polymer that can be recovered to ambient conditions. While this transformation can occur without additional stimuli, experimental observations have shown that laser irradiation can induce a similar transformation at reduced pressure. The resulting polymeric phase, which is metastable under ambient conditions, releases energy through decomposition into more stable configurations. Using time-dependent density functional theory and Born-Oppenheimer molecular dynamics simulations, we investigate the mechanism by which electronic excitation facilitates CO polymerization. Our calculations reveal that electronic excitation enhances carbon-carbon bonding, enabling polymerization at pressures significantly lower than those required by conventional compression methods. These findings suggest that a photo-assisted approach could be employed to synthesize novel, potentially energetic materials under less demanding pressure conditions.