Functional and Basis Set Dependence for Time‐Dependent Density Functional Theory Trajectory Surface Hopping Molecular Dynamics: Cis‐Azobenzene Photoisomerization

Abstract

Within three functionals (TD‐B3LYP, TD‐BHandHLYP, and TD‐CAM‐B3LYP) in combination with four basis sets (3‐21g, 6‐31g, 6‐31g(d), and cc‐pvdz), global switching (GS) trajectory surface hopping molecular dynamics has been performed for cis‐to‐trans azobenzene photoisomerization up to the S1(nπ*) excitation. Although all the combinations show artificial double‐cone structure of conical intersection between ground and first excited states, simulated quantum yields and lifetimes are in good agreement with one another; 0.6 (±5%) and 40.5 fs (±10%) by TD‐B3LYP, 0.5 (±10%) and 35.5 fs (±4%) by TD‐BHandHLYP, and 0.44 (±9%) and 35.2 fs (±10%) by TD‐CAM‐B3LYP. By analyzing distributions of excited‐state population decays, hopping spots, and typical trajectories with performance of 12 functional/basis set combinations, it has been concluded that functional dependence for given basis set is slightly more sensitive than basis set dependence for given functional. The present GS on‐the‐fly time‐dependent density functional theory (TDDFT) trajectory surface hopping simulation can provide practical benchmark guidelines for conical intersection driven excited‐state molecular dynamics simulation involving in large complex system within ordinary TDDFT framework. © 2019 Wiley Periodicals, Inc.

cis → trans photoisomerisation of azobenzene: a fresh theoretical look

“…The cis → trans photo-isomerisation has been much less investigated, with fewer theoretical studies dedicated to this process. 18,20,25,[35][36][37][38] Of these, even fewer 18,20 investigate isomerisation after excitation at different wavelengths to both the nπ * and ππ * states (see below). The QYs for the cis → trans isomerisation are in general higher than those of trans → cis, 39 but the dependency of QY on wavelength is less clear, varying notably from study to study.…”

The Protection of Crocin Against Ulcerative Colitis and Colorectal Cancer via Suppression of NF-κB-Mediated Inflammation

“…The 3D structure of crocin was optimized by Gaussian 09 software (Ali et al, 2020) at 6-31G* set (Ye et al, 2020). And then crocin was docked to NF-κB (the 3D structure of NF-κB was built by Swiss model software 1 ) using AutoDock 4.2 software (Liu et al, 2019;Umesh et al, 2020).…”

Trajectory surface hopping molecular dynamics on Chemiluminescence of cyclic peroxides

“…[53][54][55] Along with the wavefunction overlap evaluations [34,35,56] and analytical NACVs in the framework of linear-response TDDFT (LR-TDDFT) were derived and implemented in several quantum chemistry software packages, [57][58][59][60] the TSH-MD combing LR-TDDFT is also developed in recent years [34,59,61,62] and has been widely used to study photo-induced photochemical and photophysical processes in all areas of quantum chemistry studies from fundamentals to material and biological. [26,33,60,[63][64][65][66][67][68][69][70][71] Nevertheless, certain inherent problems limit the utility of traditional LR-TDDFT for CL and must be carefully considered in an practical TSH-MD simulations for CL reactions. First, traditional LR-TDDFT with a restricted closed-shell reference state cannot describe the multiconfigurational properties in chemiluminescent reactions which have to involve a ground-state open-shell biradical or radical pairs.…”