Exploring a free energy landscape by means of multidimensional infrared and terahertz spectroscopies

Abstract

A model for the dipolar crystal system is employed to explore a role of free energy landscape (FEL), in which dipolar molecules are posted on two-dimensional lattice sites with two-state libratinal dynamics. All dipole-dipole interactions are included to have frustrated interactions among the dipoles. For the regular and distorted lattice cases, the FEL is calculated from the interaction energies and the total polarizations for all possible dipolar states at various temperatures. At high temperatures, the shape of the calculated FEL is smooth and parabolic, while it becomes bumpy at low temperatures exhibiting multiple local minima. To study dynamical aspects of the system, the single flip dynamics and the single-double mixed flips dynamics of dipoles are examined from a master equation approach. As the observables of linear absorption and two-dimensional (2D) infrared, far infrared, and terahertz spectroscopies, the first- and third-order response functions of polarization are calculated for different physical conditions characterized by the FEL. While the linear absorption signals decay in time in a similar manner regardless of the FEL profiles, the 2D signals exhibit prominent differences for those profiles. This indicates that we may differentiate the FEL profiles by changing two-time valuables in 2D spectroscopy. As illustrated in the single-double flips case, the FEL study by means of 2D spectroscopy, however, relies on the dynamics which is set independently from the FEL. The Smoluchowski equation is applied to examine the description of the collective dynamics on the microscopically calculated FEL. We found that the one-dimensional and 2D signals calculated from the Smoluchowski equation agree with those from master equation only at temperatures where the FEL becomes parabolic shape.