The correct treatment of vibronic effects is vital for the modeling of absorption spectra of solvated dyes, as many prominent spectral features can often be ascribed to vibronic transitions. Vibronic spectra can be computed within the Franck-Condon approximation for small dyes in solution using an implicit solvent model. However, implicit solvent models neglect specific solute-solvent interactions and provide only an approximate treatment of solvent polarization effects. Furthermore, temperature-dependent solvent broadening effects are often only accounted for using a broadening parameter chosen to match experimental spectra. On the other hand, ensemble approaches provide a straightforward way of accounting for solute-solvent interactions and temperature-dependent broadening effects by computing vertical excitation energies obtained from an ensemble of solute-solvent conformations. However, ensemble approaches do not explicitly account for vibronic effects and often produce spectral shapes in poor agreement with experiment. We address these shortcomings by combining the vibronic fine structure of an excitation obtained in the Franck-Condon picture at zero temperature with vertical excitations computed for a room-temperature ensemble of solute-solvent configurations. In this combined approach, all temperature-dependent broadening is therefore treated classically through the sampling of configurations, with vibronic contributions included as a zero-temperature correction to each vertical transition. We test the proposed method on Nile Red and the green fluorescent protein chromophore in polar and non-polar solvents. For systems with strong solute-solvent interaction, the approach yields a significant improvement over the ensemble approach, whereas for systems with weaker interactions, both the shape and the width of the spectra are in excellent agreement with experiment.
Vibronic fine structure in the nitrogen 1s photoelectron spectra from Franck-Condon simulations. III. Rules for amine/imine N atoms in small N-heterocycles
Franck-Condon Simulation of Vibrationally-Resolved X-ray Spectra for Diatomic Systems: Validation of Harmonic Approximation and Density Functional Theory
Electronic friction near metal surfaces: a case where molecule-metal couplings depend on nuclear coordinates
在分子-金属耦合依赖于核坐标的一般情况下，我们推导出了一个明确的形式的电子摩擦的感觉由一个分子附近的金属表面。我们的工作概括了von Oppen等人的先前研究[Beilstein Journal of Nanotechnology，3，144，2012]，其中我们现在超越了Condon近似（即分子-金属耦合不保持恒定）。使用绝热极限下的非平衡格林函数形式，我们表明波动的金属分子耦合会导致新的摩擦阻尼项和随机力，以及对平均力势的修正。数值试验进行了修改后的经典主方程相比，我们的结果表明，违反康登近似动力学可以有很大的影响。
