Time Correlation Function Modeling of Third-Order Sum Frequency Vibrational Spectroscopy of a Charged Surface/Water Interface.

Sum frequency vibrational spectroscopy (SFVS), a second-order optical process, is interface-specific in the dipole approximation [Perry, A.; Neipert, C.; Moore, P.; Space, B. Chem. Rev. 2006, 106, 1234-1258; Richmond, G. L. Chem. Rev. 2002, 102, 2693-2724; Byrnes, S. J.; Geissler, P. L.; Shen, Y. R. Chem. Phys. Lett. 2011, 516, 115-124]. At charged interfaces, the experimentally detected signal is a combination of enhanced second-order and static-field-induced third-order contributions due to the existence of a static field. Evidence of the importance/relative magnitude of this third-order contribution is seen in the literature [Ong, S.; Zhao, X.; Eisenthal, K. B. Chem. Phys. Lett. 1992, 191, 327-335; Zhao, X.; Ong, S.; Eisenthal, K. B. Chem. Phys. Lett. 1993, 202, 513-520; Shen, Y. R. Appl. Phys. B: Laser Opt. 1999, 68, 295-300], but a molecularly detailed approach to separately calculating the second- and third-order contributions is difficult to construct. Recent work presented a novel molecular dynamics (MD)-based theory that provides a direct means to calculate the third-order contributions to SFVS spectra at charged interfaces [Neipert, C.; Space, B. J. Chem. Phys. 2006, 125, 224706], and a hyperpolarizability model for water was developed as a prerequisite to practical implementation [Neipert, C.; Space, B. Comput. Lett. 2007, 3, 431-440]. Here, these methods are applied to a highly abstracted/idealized silica/water interface, and the results are compared to experimental data for water at a fused quartz surface. The results suggest that such spectra have some quite general spectral features.