Excited-State Dynamics in SO2: II. The Role of Triplet States in the Bound State Relaxation Studied by Surface-Hopping Simulations

Abstract

The importance of triplet states in the photorelaxation dynamics of SO2 is studied by mixed quantum-classical dynamics simulations. Using the Surface Hopping including ARbitrary Couplings (Sharc) method, intersystem crossing processes caused by spin-orbit coupling are found occuring on an ultrafast time scale (few 100 fs) and thus competing with internal conversion. While in the singlet-only dynamics only oscillatory population transfer between the 1B1 and 1A2 states is observed, in the dynamics including singlet and triplet states we find additionally continuous ISC to the 3B2 state and to a smaller extent to the 3B1/3A2 coupled states. The populations obtained from the dynamics are discussed with respect to the overall nuclear motion and in the light of recent TRPEPICO studies [Wilkinson et al., paper I].

12 pages, 9 figures

References in corpus (4)

• Femtosecond Intersystem Crossing in the DNA Nucleobase Cytosine
• A singlet and triplet excited-state dynamics study of the keto and enol tautomers of cytosine
• Nonadiabatic ab initio molecular dynamics including spin-orbit coupling and laser fields
• Theoretical prediction of the importance of the 3B2 state in the dynamics of sulfur dioxide

Cited by in corpus (7)

• A general method to describe intersystem crossing dynamics in trajectory surface hopping
• Surface Hopping Dynamics Including Intersystem Crossing using the Algebraic Diagrammatic Construction Method
• Perturbational treatment of spin-orbit coupling for generally applicable high-level multi-reference methods
• Validating Fewest-Switches Surface Hopping in the Presence of Laser Fields
• Time-resolving the UV-initiated photodissociation dynamics of OCS
• Simultaneous imaging of vibrational, rotational, and electronic wave packet dynamics in a triatomic molecule
• Ultrafast Intersystem Crossing in SO${}_2$ and Nucleobases