Chiral surfaces

An important distinction among surfaces and interfaces is whether or not they exliibit mirror synnnetry about a plane nonnal to the surface. This synnnetry is particularly relevant for the case of isotropic surfaces (co-synnnetry), i.e. ones that are equivalent in every azunuthal direction. Those surfaces that fail to exliibit mirror synnnetry may be tenned chiral surfaces. They would be expected, for example, at the boundary of a liquid comprised of chiral molecules. Magnetized surfaces of isotropic media may also exliibit this synnnetry. (For a review of SFIG studies of chiral interfaces, the reader is referred to [68]. ... 

Given the interest and importance of chiral molecules, there has been considerable activity in investigating die corresponding chiral surfaces [, and 70]. From the point of view of perfomiing surface and interface spectroscopy with nonlinear optics, we must first examhie the nonlinear response of tlie bulk liquid. Clearly, a chiral liquid lacks inversion synnnetry. As such, it may be expected to have a strong (dipole-allowed) second-order nonlinear response. This is indeed true in the general case of SFG [71]. For SHG, however, the pemiutation synnnetry for the last two indices of the nonlinear susceptibility tensor combined with the... 

The surface susceptibility tensor of a chiral surface possesses different symmetry properties as compared to the surface susceptibility tensor of an isotropic surface. The main difference for a chiral surface arises from the axes OX and the O Y, the two axes in the plane of the surface, which are no longer indistinguishable. The nonvanishing elements of the susceptibility tensor are then [52] ... 

Only for achiral surfaces does the last tensor element vanish altogether. Equation (4) retains a similar form but now accommodates a new tensor element. To date, very few experimental works have been reported on chiral surfaces, although the nonlinear effects are expected to be rather large [51]. 

Prochiral Molecules Interacting with Chiral Surfaces... 

In principle, sites a, IT, and c need not be association sites as depicted by Ogston but could be steric sites that form obstructions such that the adsorbed molecule is chirally directed. Only one active site is actually required providing the remaining two sites (protuberances or cavities) are different from each other and from the active site that catalyzes the reaction. They could be identical providing they are not symmetrically oriented with respect to the active site (not an isosceles triangle). These are the basic concepts for a chiral environment on a surface and they lead to the three basic methods for creating chiral surfaces in heterogeneous catalysis. 

Shinitzky M and Haimovitz R. 1993. Chiral surfaces in micelles of enantiomeric /V-palmitoyl- and JV-stearoylserine. Journal of the American Chemical Society 115 12545-12549. 

The screw models of Figure 7.4 are, of course, an abstraction, and real macromolecules are much more complex. In particular, apart from DNA and G-wires, which have sugar-phosphate backbones as external ridges, but are also charged, most natural and synthetic polymers have external side chains which could generate a secondary chiral surface, which might interfere with the chirality of the polymer backbone.28 Even if the qualitative estimate of Sq based on the models of Figure 7.4 seems rather primitive, the estimate of Hq... 

Comparison of Linearly and Circularly Polarized Probes of Nonlinear Optical Activity of Chiral Surfaces... 

Figure 9.9 Simulated normalized line shapes of -polarized (a-c) and p-polarized (if-/) second-harmonic signals for quarter waveplate measurements (a) and (if) hypothetical achiral surface (hs = 0.5 fp = 0.75, gp = —0.5), (b) and (if) hypothetical chiral surface with in-phase chiral coefficient (fs = 0.75, hs = 0.5 fp = 0.75, gp = —0.5, hp = 0.25), (c) and (/) hypothetical chiral surface with out-of-phase chiral coefficient ( fs = 0.75 0.25i, hs = 0.5 fp = 0.75, gp = —0.5, hp = 0.25z). Upper (solid line) and lower (dashed line) sign in expansion coefficients correspond to two enantiomers. Rotation angles of 45° and 225° (135° and 315°) correspond to right-hand (left-hand) circularly polarized light and are indicated for one of enantiomers with open and filled circles, respectively.

Figure 9.17 Geometry of second-harmonic generation from chiral surface. Two orientations of sample are related by coordinate transformation x -> x, y - —y, and z -> —z.

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