Investigating the Photodynamics of trans-Azobenzene with Coupled Trajectories

• DOI: 10.1021/acs.jctc.3c00978
• Publication Date: 2024-01-05T04:06:11Z
• Authors: Carlotta Pieroni; Eduarda Sangiogo Gil; Lea M. Ibele; Maurizio Persico; Giovanni Granucci; Federica Agostini

In this work, we present the first implementation of the coupled-trajectory Tully surface hopping (CT-TSH) suitable for applications to molecular systems. We combine CT-TSH with the semiempirical Floating Occupation Molecular Orbitals-Configuration Interaction (FOMO-CI) electronic structure method to investigate the photoisomerization dynamics of trans-azobenzene. Our study shows that CT-TSH can capture correctly decoherence effects in this system, yielding consistent electronic and nuclear dynamics in agreement with (standard) decoherence-corrected TSH. Specifically, CT-TSH is derived from the exact factorization and the electronic coefficients’ evolution is directly influenced by the coupling of trajectories, resulting in the improvement of internal consistency if compared to standard TSH.