Kinetics and thermodynamics of electron transfer in Debye solvents: An analytical and nonperturbative reduced density matrix theory

A nonperturbative electron transfer rate theory is developed based on the reduced density matrix dynamics, which can be evaluated readily for the Debye solvent model without further approximation. Not only does it recover for reaction rates the celebrated Marcus' inversion and Kramers' turnover behaviors, the present theory also predicts for reaction thermodynamics, such as equilibrium Gibbs free-energy and entropy, some interesting solvent-dependent features that are calling for experimental verification. Moreover, a continued fraction Green's function formalism is also constructed, which can be used together with Dyson equation technique, for efficient evaluation of nonperturbative reduced density matrix dynamics.Comment: 8 pages, 5 figures. J. Phys. Chem. B, accepte

用Pump-dump-probe瞬态吸收光谱监测分子高振动激发态动力学

给出了监测外场激发下分子动力学过程的瞬态吸收信号的确切理论表述。在数值计算中，采用Ｉ２的一个二势能面系统，得到了监测基电子态高振动激发波包的吸收光谱。Ｉ２的Ｂ电子激发态用作双光子ｐｕｍｐ－ｄｕｍｐ过程的中间态。提出了一个二阶差谱探测方案，即从弱响应区域的５阶（ｐｕｍｐ－ｄｕｍｐ－ｐｒｏｂｅ）非线性光谱中提取分子动力学信息