基于非谐系统势的Caldeira-Leggett模型的振动光谱
Vibrational spectroscopy via the Caldeira-Leggett model with anharmonic system potentials
摘要：
Caldeira-Leggett（CL）模型描述了一个与谐波池双线性耦合的系统，由于其极其简单，在凝聚相光谱学中受到欢迎。然而，由于可逆性问题的存在，该模型对具有非谐系统势的情况的适用性是有疑问的，因为它是描述溶液中的实际系统所需要的[J. Phys. Chem. Lett.，\textbf{6}，2722（2015）]，除非系统本身类似于CL模型形式。这很可能是在表面或在固体制度的情况下，我们在这里确认的一个特定的例子，碘分子在原子氩环境下的高压。为此，我们扩展了最近提出的用于参数化线性广义Langevin动力学的傅立叶方法[J. Chem. Phys.，\textbf{142}，244110（2015）]中的方法应用于基于CL模型的非线性情况，并进行广泛的误差分析。为了预先判断该模型的适用性，我们给出了简便的经验判据，并讨论了势重整化项的影响。所获得的结果提供的证据表明，CL模型可以用于描述一个潜在的广泛的系统类。
英文摘要：
The Caldeira-Leggett (CL) model, which describes a system bi-linearly coupled to a harmonic bath, has enjoyed popularity in condensed phase spectroscopy owing to its utmost simplicity. However, the applicability of the model to cases with anharmonic system potentials, as it is required for the description of realistic systems in solution, is questionable due to the presence of the invertibility problem [J. Phys. Chem. Lett., \textbf{6}, 2722 (2015)] unless the system itself resembles the CL model form. This might well be the case at surfaces or in the solid regime, which we here confirm for a particular example of an iodine molecule in the atomic argon environment under high pressure. For this purpose we extend the recently proposed Fourier method for parameterizing linear generalized Langevin dynamics[J. Chem. Phys., \textbf{142}, 244110 (2015)] to the non-linear case based on the CL model and perform an extensive error analysis. In order to judge on the applicability of this model in advance, we give handy empirical criteria and discuss the effect of the potential renormalization term. The obtained results provide evidence that the CL model can be used for describing a potentially broad class of systems.
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