Direct calculation of the temperature dependence of 2D-IR spectra: Urea in water

A method for directly calculating the temperature derivative of two-dimensional infrared (2D-IR) spectra from simulations at a single temperature is presented. The approach is demonstrated by application to the OD stretching spectrum of isotopically dilute aqueous (HOD in H2O) solutions of urea as a function of concentration. Urea is an important osmolyte because of its ability to denature proteins, which has motivated significant interest in its effect on the structure and dynamics of water. The present results show that the temperature dependence of both the linear IR and 2D-IR spectra, which report on the underlying energetic driving forces, is more sensitive to urea concentration than the spectra themselves. Additional physical insight is provided by calculation of the contributions to the temperature derivative from different interactions, e.g., water-water, water-urea, and urea-urea, present in the system. Finally, it is demonstrated how 2D-IR spectra at other temperatures can be obtained from only room temperature simulations.

Automated summary

This paper presents a method for directly calculating the temperature derivative of 2D-IR spectra. The approach is demonstrated by studying the OD stretching spectrum of urea in isotopically dilute aqueous solutions. The results show that the temperature dependence of the spectra is more sensitive to urea concentration than the spectra themselves. Additional insight is provided by calculating the contributions to the temperature derivative from different interactions present in the system. It is also shown how 2D-IR spectra at other temperatures can be obtained from room temperature simulations.