44 research outputs found
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Statistical mechanics of sum frequency generation spectroscopy for the liquid-vapor interface of dilute aqueous salt solutions
We demonstrate a theoretical description of vibrational sum frequency generation (SFG) at the boundary of aqueous electrolyte solutions. This approach identifies and exploits a simple relationship between SFG lineshapes and the statistics of molecular orientation and electric field. Our computer simulations indicate that orientational averages governing SFG susceptibility do not manifest ion-specific shifts in local electric field, but instead, ion-induced polarization of subsurface layers. Counterbalancing effects are obtained for monovalent anions and cations at the same depth. Ions held at different depths induce an imbalanced polarization, suggesting that ion-specific effects can arise from weak, long ranged influence on solvent organization
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Toward a simple molecular understanding of sum frequency generation at air-water interfaces
Second-order vibrational spectroscopies successfully isolate signals from interfaces, but they report on intermolecular structure in a complicated and indirect way. Here we adapt a perspective on vibrational response developed for bulk spectroscopies to explore the microscopic fluctuations to which sum frequency generation (SFG), a popular surface-specific measurement, is most sensitive. We focus exclusively on inhomogeneous broadening of spectral susceptibilities for OH stretching of HOD as a dilute solute in D{sub 2}O. Exploiting a simple connection between vibrational frequency shifts and an electric field variable, we identify several functions of molecular orientation whose averages govern SFG. The frequency-dependence of these quantities is well captured by a pair of averages, involving alignment of OH and OD bonds with the surface normal at corresponding values of the electric field. The approximate form we obtain for SFG susceptibility highlights a dramatic sensitivity to the way a simulated liquid slab is partitioned for calculating second-order response
A diagrammatic formulation of the kinetic theory of fluctuations in equilibrium classical fluids. VI. Binary collision approximations for the memory function for self correlation functions
We use computer simulation results for a dense Lennard-Jones fluid for a
range of temperatures to test the accuracy of various binary collision
approximations for the memory function for density fluctuations in liquids. The
approximations tested include the moderate density approximation of the
generalized Boltzmann-Enskog memory function (MGBE) of Mazenko and Yip, the
binary collision approximation (BCA) and the short time approximation (STA) of
Ranganathan and Andersen, and various other approximations derived by us using
diagrammatic methods. The tests are of twotypes. The first is a comparison of
the correlation functions predicted by each approximate memory function with
the simulation results, especially for the self longitudinal current
correlation function (SLCC). The second is a direct comparison of each
approximate memory function with a memory function numerically extracted from
the correlation function data. The MGBE memory function is accurate at short
times but decays to zero too slowly and gives a poor description of the
correlation function at intermediate times. The BCA is exact at zero time, but
it predicts a correlation function that diverges at long times. The STA gives a
reasonable description of the SLCC but does not predict the correct temperature
dependence of the negative dip in the function that is associated with caging
at low temperatures. None of the other binary collision approximations is a
systematic improvement upon the STA. The extracted memory functions have a
rapidly decaying short time part, much like the STA, and a much smaller, more
slowly decaying part of the type predicted by mode coupling theory. Theories
that use mode coupling commonly include a binary collision term in the memory
function but do not discuss in detail the nature of that term. ...Comment: 18 pages, 10 figure
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Toward a simple molecular understanding of sum frequency generation at air-water interfaces
Recommended from our members