Direct nonadiabatic quantum dynamics simulations of the photodissociation of phenol

被引：14

作者：

Christopoulou, Georgia ^{[1
]}

Tran, Thierry ^{[1
,2
]}

Worth, Graham A. ^{[1
]}

机构：

[1] UCL, Dept Chem, London WC1H 0AJ, England

[2] Imperial Coll London, Dept Chem, White City Campus, London W12 0BZ, England

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2021年 / 23卷 / 41期

关键词：

POTENTIAL-ENERGY SURFACES; AROMATIC-MOLECULES; NUCLEAR MOTION; PHOTOCHEMISTRY; STATES; DETACHMENT; PHOTOLYSIS; ALGORITHM; ELECTRON; SYSTEM;

D O I：

10.1039/d1cp01843d

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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)pi pi, 1(1)pi pi*, 1(1)pi sigma*, 2(1)pi sigma*, 2(1)pi pi*, 3(1)pi pi*), 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)pi pi/1(1)pi sigma* conical intersection.

引用

页码：23684 / 23695

页数：12