Mitrić Roland, Werner Ute, Bonacić-Koutecký Vlasta
Institut fur Chemie, Humboldt-Universitat zu Berlin, Brook-Taylor-Strasse 2, D-12489 Berlin, Germany.
J Chem Phys. 2008 Oct 28;129(16):164118. doi: 10.1063/1.3000012.
We present a theoretical approach for the nonadiabatic dynamics "on the fly" based on the combination of the time-dependent density functional theory (TDDFT) with Tully's stochastic surface hopping method. Our formulation is based on localized Gaussian basis sets and is suitable for the simulation of ultrafast processes in complex molecular systems including all degrees of freedom. Our approach is used for the simulation of time resolved photoelectron spectra in the framework of the Wigner distribution approach. In order to illustrate the scope of the method, we study the ultrafast photoswitching dynamics of the prototype Schiff base benzylideneaniline (BAN). The nonradiative lifetime of the S(1) state of BAN is determined to be approximately 200 fs. The mechanism of the photoisomerization has been investigated and a connection between the time resolved photoelectron signal and the underlying nonadiabatic processes has been established.
我们提出了一种基于含时密度泛函理论（TDDFT）与塔利随机表面跳跃方法相结合的“即时”非绝热动力学理论方法。我们的公式基于局域化高斯基组，适用于模拟包括所有自由度在内的复杂分子系统中的超快过程。我们的方法用于在维格纳分布方法框架内模拟时间分辨光电子能谱。为了说明该方法的适用范围，我们研究了原型席夫碱苄叉苯胺（BAN）的超快光开关动力学。BAN的S(1)态的非辐射寿命确定约为200飞秒。研究了光异构化的机制，并建立了时间分辨光电子信号与潜在非绝热过程之间的联系。
