Over the last decades, theoretical photochemistry has produced multiple techniques to simulate the nonadiabatic dynamics of molecules. Surprisingly, much less effort has been devoted to adequately describing the first step of a photochemical or photophysical process: photoexcitation. Here, we propose a formalism to include the effect of a laser pulse in trajectory-based nonadiabatic dynamics at the level of the initial conditions, with no additional cost. The promoted density approach (PDA) decouples the excitation from the nonadiabatic dynamics by defining a new set of initial conditions, which include an excitation time. PDA with surface hopping leads to nonadiabatic dynamics simulations in excellent agreement with quantum dynamics using an explicit laser pulse and highlights the strong impact of a laser pulse on the resulting photodynamics and the limits of the (sudden) vertical excitation. Combining PDA with trajectory-based nonadiabatic methods is possible for any arbitrary-sized molecules using a code provided in this work.
Ultrafast Photodissociation Dynamics and Nonadiabatic Coupling Between Excited Electronic States of Methanol Probed by Time-Resolved Photoelectron Spectroscopy
通过对时间分辨光电子能谱学实验的详细分析和电子结构计算，研究了甲醇在156 nm光激发下的电子和核动力学.光激发泵浦脉冲之后是延迟的260 nm光电离探测脉冲，以产生通过速度图成像分析的光电子。质量分辨离子的产率，测量与类似的实验条件下，被发现表现出相同的时间依赖性作为特定的光电子能谱特征。能量分辨信号的起始和衰减时间从测量的光电子谱中提取，以实现高的时间分辨率，超过20 fs的泵浦和探测脉冲持续时间。当结合{ \it ab initio}计算选定的削减通过激发态势能面，这一信息允许动态的瞬态激发分子，表现出多个核和电子的自由度，以跟踪其固有的几个飞秒的时间尺度。在15 fs的光激发范围内，我们观察到了2 $^{1}$ A $''$（S $_2$）电子态与1 $^{1}$ A $'$（S $_3$）电子态的锥形交叉，揭示了原子核在C-O伸缩和C-O-H角打开后的光解路径.
Analysis of Trajectory Similarity and Configuration Similarity in On-the-Fly Surface-Hopping Simulation on Multi-Channel Nonadiabatic Photoisomerization Dynamics
Quasi-classical Trajectory Calculations on a Two-state Potential Energy Surface Including Nonadiabatic Coupling Terms as Friction for D+ + H2 Collisions
Spectroscopic photorelaxation signatures in pyrazine from nonadiabatic dynamics simulations with coupled cluster theory
Norwegian University of Science and Technology（挪威科技大学）；European XFEL（欧洲XFEL）；Stanford University（斯坦福大学）；SLAC National Accelerator Laboratory（SLAC国家加速器实验室）
Flexible Framework for Surface Hopping: From Hybrid Schemes for Machine Learning to Benchmarkable Nonadiabatic Dynamics
Academy of Sciences of the Czech Republic（捷克科学院）；University of Warsaw（华沙大学）；Indian Institute of Technology, Guwahati（印度理工学院古瓦哈提分校）；College of Chemistry and Chemical Engineering（化学与化学工程学院）
Perspective on a challenge: predicting the photochemistry of cyclobutanone
University of Bristol（布里斯托大学）；University of Chemistry and Technology, Prague（布拉格化工大学）；University of Birmingham（伯明翰大学）；KTH Royal Institute of Technology（瑞典皇家理工学院）；Stony Brook University（石溪大学）；Aix Marseille University（艾克斯-马赛大学）；Institut Universitaire de France（法国高等研究院）；University College London（伦敦大学学院）；Newcastle University（纽卡斯尔大学）；Stanford University（斯坦福大学）
Quantum mechanical and quasiclassical investigation of the time domain nonadiabatic dynamics of NO2 close to the bottom of the X2A1-A2B2 conical intersection
Computing linear optical spectra in the presence of nonadiabatic effects on Graphics Processing Units using molecular dynamics and tensor-network approaches
Excited-state nonadiabatic dynamics in explicit solvent using machine learned interatomic potentials
Research Platform on Accelerating Photoreaction Discovery (ViRAPID), University of Vienna（维也纳大学加速光反应发现研究平台（ViRAPID））；Vienna Doctoral School in Chemistry, University of Vienna（维也纳大学维也纳化学博士学院）；Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna（维也纳大学化学学院理论化学研究所）；Department of Chemistry, Sapienza University of Rome（罗马大学化学系）；Wilhelm-Ostwald Institute, University of Leipzig（莱比锡大学威廉·奥斯特瓦尔德研究所）
An Automated Framework for Analyzing Structural Evolution in On-the-fly Non-adiabatic Molecular Dynamics Using Autoencoder and Multiple Molecular Descriptors
A CASSCF/MRCI Trajectory Surface Hopping Simulation of the Photochemical Dynamics and the Gas Phase Ultrafast Electron Diffraction Patterns of Cyclobutanone
Predicting the photodynamics of cyclobutanone triggered by a laser pulse at 200 nm and its MeV-UED signals -- a trajectory surface hopping and XMS-CASPT2 perspective
