A time correlation function theory describing static field enhanced third order optical effects at interfaces.

Sum vibrational frequency spectroscopy, a second order optical process, is interface specific in the dipole approximation. At charged interfaces, there exists a static field, and as a direct consequence, the experimentally detected signal is a combination of enhanced second and static field induced third order contributions. There is significant evidence in the literature of the importance/relative magnitude of this third order contribution, but no previous molecularly detailed approach existed to separately calculate the second and third order contributions.

A theoretical description of the polarization dependence of the sum frequency generation spectroscopy of the water/vapor interface.

An improved time correlation function (TCF) description of sum frequency generation (SFG) spectroscopy was developed and applied to theoretically describing the spectroscopy of the ambient water/vapor interface. A more general TCF expression than was published previously is presented-it is valid over the entire vibrational spectrum for both the real and imaginary parts of the signal. Computationally, earlier time correlation function approaches were limited to short correlation times that made signal processing challenging.

Identification of a wagging vibrational mode of water molecules at the water/vapor interface.

An improved time correlation function description of sum frequency generation (SFG) spectroscopy was applied to theoretically describe the water/vapor interface. The resulting spectra compare favorably in shape and relative magnitude to extant experimental results in the O-H stretching region of water. Further, the SFG spectra show a well-defined intermolecular mode at 875 cm(-1) that has significant intensity.

A time correlation function theory of two-dimensional infrared spectroscopy with applications to liquid water.

A theory describing the third-order response function R((3))(t(1),t(2),t(3)), which is associated with two-dimensional infrared (2DIR) spectroscopy, has been developed. R((3)) can be written as sums and differences of four distinct quantum mechanical dipole (multi)time correlation functions (TCF's), each with the same classical limit; the combination of TCF's has a leading contribution of order variant Planck's over 2pi (3) and thus there is no obvious classical limit that can be written in terms of a TCF. In order to calculate the response function in a form amenable to classical mechanical simulation techniques, it is rewritten approximately in terms of a single classical TCF, B(R)(t(1),t(2),t(3))=micro(j)(t(2)+t(1))micro(i)(t(3)+t(2)+t(1))micro(k)(t(1))micro(l)(0), where the subscripts denote the Cartesian dipole directions.