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. The resonance is due to a wagging mode localized on a single water molecule. It represents a well-defined population of water molecules at the interface that, along with the free O-H modes, represent the dominant interfacial species.

A new theory for the fifth order Raman response function, R(5)(t1,t2), is presented. Using this result, R(5)(t1,t2) is shown to have a classical limit given by a combination of time derivatives of the real and imaginary parts of a two time correlation function (TCF) of the polarizability. In contrast with one time correlation functions, no exact analytic relationship exists between the real and imaginary parts of the quantum mechanical TCF that would allow the classical limit to be written in terms of classical TCF’s. Writing the nonlinear response function in terms of classical TCF’s would allow R(5)(t1,t2) to be calculated with minimal computational effort, in contrast to existing (exact) classical formulations. However, a simple approximate relationship is shown to exist between the real and imaginary parts of the two time TCF for a harmonic system with nonlinear polarizability. In the spirit of quantum correction, this relationship is used to write the exact classical response function in terms of classical TCF’s. The resulting TCF expression is then calculated from (fully anharmonic) molecular dynamics calculations supplemented by a suitable spectroscopic (polarizability) model. The approximate expression is demonstrated to have correct limiting behaviors and leads to a two-dimensional spectrum for ambient carbon disulfide in excellent agreement with existing experimental and theoretical work. The proposed approach makes the calculation of fifth order response functions practical for a wide variety of chemically interesting systems.

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. The response function is then given, in the frequency domain, as the Fourier transform of a classical TCF multiplied by frequency factors. This classical expression can then further be quantum corrected to approximate the true response function, although for low frequency spectroscopy no correction is needed. In the classical limit, R((3)) becomes the sum of multidimensional time derivatives of B(R)(t(1),t(2),t(3)). To construct the theory, the response function's four TCF's are rewritten in terms of a single TCF: first, two TCF's are eliminated from R((3)) using frequency domain detailed balance relationships, and next, two more are removed by relating the remaining TCF's to each other within a harmonic oscillator approximation; the theory invokes a harmonic approximation only in relating the TCF's and applications of theory involve fully anharmonic, atomistically detailed molecular dynamics (MD). Writing the response function as a single TCF thus yields a form amenable to calculation using classical MD methods along with a suitable spectroscopic model. To demonstrate the theory, the response function is obtained for liquid water with emphasis on the OH stretching portion of the spectrum. This approach to evaluating R((3)) can easily be applied to chemically interesting systems currently being explored experimentally by 2DIR and to help understand the information content of the emerging multidimensional spectroscopy.

Nonlinear spectroscopy provides insights into dynamics, but the response functions required for its interpretation pose a challenge to theorists. We proposed an approach in which the fifth-order response function [R5( t1, t2)] was expressed as a two-time classical time correlation function (TCF). Here, we present TCF theory results for R5( t1, t2) in liquid xenon. Using a first-order dipole-induced dipole polarizability model, the result is compared to an exact numerical calculation showing remarkable agreement. In addition, R5( t1, t2) is calculated using the exactly solved polarizability model, yielding different results and predicting an echo signal.

Multidimensional spectroscopy has the ability to provide great insight into the complex dynamics and time-resolved structure of liquids. Theoretically describing these experiments requires calculating the nonlinear-response function, which is a combination of quantum-mechanical time correlation functions R5(t1,t2) was expressed with a two-time, computationally tractable, classical TCF. Writing the response function in terms of classical TCFs brings the full power of atomistically detailed molecular dynamics to the problem. In this paper, the new TCF theory is employed to calculate the fifth-order Raman response function for liquid xenon and investigate several of the polarization conditions for which experiments can be performed on an isotropic system. The theory is shown to reproduce line-shape characteristics predicted by earlier theoretical work.