Direct nonadiabatic quantum dynamics simulations of the photodissociation of phenol. Issue 41 (13th October 2021)

• Record Type: Journal Article
• Authors: Christopoulou, Georgia; Tran, Thierry; Worth, Graham A.
• Is Part Of: Physical chemistry chemical physics. Volume 23:Issue 41(2021)
• Page Start: 23684
• Page End: 23695
• Publication Date: 2021-10-13
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d1cp01843d
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Direct quantum dynamics have been used to generate coupled potential energy surfaces for the nonadiabatic photodissociation of phenol. Abstract : Gaussian wavepacket methods are becoming popular for the investigation of nonadiabatic molecular dynamics. In the present work, a recently developed efficient algorithm for the Direct Dynamics variational Multi-Configurational Gaussian (DD-vMCG) method has been used to describe the multidimensional photodissociation dynamics of phenol including all degrees of freedom. Full-dimensional quantum dynamic calculations including for the first time six electronic states ( 1 ππ, 1 1 ππ*, 1 1 πσ*, 2 1 πσ*, 2 1 ππ*, 3 1 ππ*), along with a comparison to an existing analytical 4-state model for the potential energy surfaces are presented. Including the fifth singlet excited state is shown to have a significant effect on the nonadiabatic photodissociation of phenol to the phenoxyl radical and hydrogen atom. State population and flux analysis from the DD-vMCG simulations of phenol provided further insights into the decay mechanism, confirming the idea of rapid relaxation to the ground state through the 1 ππ/1 1 πσ* conical intersection.