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Title: 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 H 2 O) 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.  more » « less
Award ID(s):
2102656 2117449 1950293
PAR ID:
10414565
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
The Journal of Chemical Physics
Volume:
158
Issue:
6
ISSN:
0021-9606
Page Range / eLocation ID:
064507
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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