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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.
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A generalized van’t Hoff relation for the temperature dependence of complex-valued nonlinear spectra
The temperature dependence of spectra can reveal important insights into the structural and dynamical behavior of the system being probed. In the case of linear spectra, this has been exploited to investigate the thermodynamic driving forces governing the spectral response. Indeed, the temperature derivative of a spectrum can be used to obtain effective energetic and entropic profiles as a function of the measured frequency. The former can further be used to predict the temperature-dependent spectrum via a van’t Hoff relation. However, these approaches are not directly applicable to nonlinear, complex-valued spectra, such as vibrational sum-frequency generation (SFG) or two-dimensional infrared (2D-IR) photon echo spectra. Here, we show how the energetic and entropic driving forces governing such nonlinear spectra can be determined and used within a generalized van’t Hoff relation to predict their temperature dependence. The central idea is to allow the underlying energetic profiles to themselves be complex-valued. We illustrate this approach for 2D-IR spectra of water and SFG spectra of the air–water interface and demonstrate the accuracy of the generalized van’t Hoff relationship and its implications for the origin of temperature-dependent spectral changes.
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- PAR ID:
- 10562770
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 161
- Issue:
- 6
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 064114
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0220236
