Kewei Sun, Luis Vasquez, Raffaele Borrelli, Lipeng Chen, Yang Zhao, Maxim F Gelin
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引用次数: 0
摘要
大多数光谱信号都是由非线性激光诱导偏振产生的。近年来,群体检测信号成为飞秒光谱学的发展趋势。偏振检测(PD)信号和群体检测信号有着本质的区别,因为它们是由作用于不同时间尺度的光诱导过程决定的。在这项工作中,我们将荧光检测(FD)N 波混合(NWM)信号视为种群检测信号的一个代表性例子,推导出该信号的严格表达式,并讨论其适合数值模拟的近似变体。这就引出了现象学 FD(PFD)信号的定义,它作为特例包含了文献中对 FD 信号的所有定义。然后,我们提出并证明了种群极化等价(PPE)定理,该定理指出,由(可能很强)激光脉冲产生的 PFD 无损检测信号可被评估为传统的 PD 信号,其中有效极化由 PFD 过渡偶极矩算子决定。我们利用 PPE 定理构建了模拟 PFD 4WM 信号的 ab initio 协议。例如,我们计算了气相吡嗪的电子二维 (2D) PFD 光谱,并将其与相应的 PD 2D 光谱进行了比较。
Interconnection between Polarization-Detected and Population-Detected Signals: Theoretical Results and Ab Initio Simulations.
Most of spectroscopic signals are specified by the nonlinear laser-induced polarization. In recent years, population-detection of signals becomes a trend in femtosecond spectroscopy. Polarization-detected (PD) and population-detected signals are fundamentally different, because they are determined by photoinduced processes acting on disparate time scales. In this work, we consider the fluorescence-detected (FD) N-wave-mixing (NWM) signal as a representative example of population-detected signals, derive a rigorous expression for this signal, and discuss its approximate variants suitable for numerical simulations. This leads us to the definition of the phenomenological FD (PFD) signal, which contains as a special case all definitions of FD signals available in the literature. Then we formulate and prove the population-polarization equivalence (PPE) theorem, which states that PFD NWM signals produced by (possibly strong) laser pulses can be evaluated as conventional PD signals in which the effective polarization is determined by the PFD transition dipole moment operator. We use the PPE theorem for the construction of the ab initio protocol for the simulation of PFD 4WM signals. As an example, we calculate electronic two-dimensional (2D) PFD spectra of the gas-phase pyrazine and compare them with the corresponding PD 2D spectra.
期刊介绍:
The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.