A new computational methodology for the characterization of complex molecular environments using IR spectroscopy: bridging the gap between experiments and computations.

The molecular interactions and dynamics of complex liquid solutions are now routinely measured using IR and 2DIR spectroscopy. In particular, the use of the latter allows the determination of the frequency fluctuation correlation function (FFCF), while the former provides us with the average frequency. In turn, the FFCF can be used to quantify the vibrational dynamics of a molecule in a solution, and the center frequency provides details about the chemical environment, solvatochromism, of the vibrational mode. In simple solutions, the IR methodology can be used to unambiguously assign the interactions and dynamics observed by a molecule in solution. However, in complex environments with molecular heterogeneities, this assignment is not simple. Therefore, a method that allows for such an assignment is essential. Here, a parametrization free method, called Instantaneous Frequencies of Molecules or IFM, is presented. The IFM method, when coupled to classical molecular simulations, can predict the FFCF of a molecule in solutions. Here, N -methylacetamide (NMA) in seven different chemical environments, both simple and complex, is used to test this new method. The results show good agreement with experiments for the NMA solvatochromism and FFCF dynamics, including characteristic times and amplitudes of fluctuations. In addition, the new method shows equivalent or improved results when compared to conventional frequency maps. Overall, the use of the new method in conjunction with molecular dynamics simulations allows unlocking the full potential of IR spectroscopy to generate molecular maps from vibrational observables, capable of describing the interaction landscape of complex molecular systems.