A Simplified Method for Theoretical Sum Frequency Generation Spectroscopy Calculation and Interpretation: the “pop model”

Sum Frequency Generation (SFG) spectroscopy is a powerful tool to probe molecular environments of oth- erwise nearly inaccessible buried interfaces. Theoretical spectroscopy is required to reveal the structure- spectroscopy relationship. Existing methods to compute theoretical spectra are restricted to the use of time- correlation functions evaluated from accurate atomistic molecular dynamics simulations, often at the ab-initio level. The interpretation of the computed spectra requires additional steps to deconvolve the spectroscopic contributions from local water and surface structural populations at the interface. The lack of a standard procedure to do this often hampers rationalization. To overcome these challenges, we rewrite the equations for spectra calculation into a sum of partial contributions from interfacial populations, weighted by their abundance at the interface. We show that SFG signatures from each population can be parameterized into a minimum dataset of reference partial spectra. Accurate spectra can then be predicted by just evaluating the statistics of interfacial populations, which can be done even with force field simulations as well as with analytic models. This approach broadens the range of simulation techniques from which theoretical spectra can be calculated, opening toward non-atomistic and Monte Carlo simulation approaches. Most notably, it allows constructing accurate theoretical spectra for interfacial conditions that can not even be simulated, as we demonstrate for the pH-dependent SFG spectra of silica/water interfaces.