The photodissociation of solvated cyclopropanone and its hydrate explored via non-adiabatic molecular dynamics using ΔSCF

The decay of cyclopropanone is a typical example of a photodecomposition process. Ethylene and carbon monoxide are formed following the excitation to the first singlet excited state through a symmetrical or asymmetrical pathway. The results obtained with non-adiabatic molecular dynamics (NAMD) using the delta self-consistent field (Delta SCF) method correspond well to previous experimental and multireference theoretical studies carried out in the gas phase. Moreover, this efficient methodology allows NAMD simulations of cyclopropanone in aqueous solution to be performed, which reveal analogue deactivation mechanisms, but a shorter lifetime and reduced photodissociation as compared to the gas-phase. The excited state dynamics of cyclopropanone hydrate, an enzyme inhibitor, in an aqueous environment are reported as well. Cyclopropanone hydrate strongly interacts with the surrounding solvent via the formation of hydrogen bonds. Excitation to the first singlet excited state shows an asymmetric pathway with cyclopropanone hydrate and propionic acid as the main photoproducts.

Automated summary

The decay of cyclopropanone is a photodecomposition process that forms ethylene and carbon monoxide through excitation to the first singlet excited state. Non-adiabatic molecular dynamics simulations in both gas phase and aqueous solution reveal similar deactivation mechanisms and different photodissociation effects.