On the Applicability of the Caldeira-Leggett Model to Condensed Phase Vibrational Spectroscopy

Abstract

Formulating a rigorous system-bath partitioning approach remains an open issue. In this context the famous Caldeira-Leggett model that enables quantum and classical treatment of Brownian motion on equal footing has enjoyed popularity. Although this model is by any means a useful theoretical tool, its ability to describe anharmonic dynamics of real systems is often taken for granted. In this Letter we show that the mapping between a molecular system under study and the model cannot be established in a self-consistent way, unless the system part of the potential is taken effectively harmonic.Mathematically, this implies that the mapping is not invertible. This `invertibility problem' is not dependent on the peculiarities of particular molecular systems under study and is rooted in the anharmonicity of the system part of the potential.

arXiv commentrevised version

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• Parametrizing linear generalized Langevin dynamics from explicit molecular dynamics simulations
• Vibrational spectroscopy via the Caldeira-Leggett model with anharmonic system potentials
• Discretized hierarchical equations of motion in mixed Liouville--Wigner space for two-dimensional vibrational spectroscopies of liquid water
• Simulating two-dimensional correlation spectroscopies with third-order infrared and fifth-order infrared--Raman processes of liquid water
• The Effect of Site-Specific Spectral Densities on the High-Dimensional Exciton-Vibrational Dynamics in the FMO Complex
• Analytical evaluation of the coefficients of the Hu-Paz-Zhang master equation: Ohmic spectral density, zero temperature, and consistency check
• On Computing Spectral Densities from Classical, Semiclassical and Quantum Simulations
• Ultrastrong coupling limit to quantum mean force Gibbs state for anharmonic environment