Orientational Dynamics of Water at an Extended Hydrophobic Interface.

We report on the orientational dynamics of water at an extended hydrophobic interface with an octadecylsilane self-assembled monolayer on fused silica. The interfacial dangling OH stretch mode is excited with a resonant pump, and its evolution followed in time by a surface-specific, vibrationally resonant, infrared-visible sum-frequency probe. High sensitivity pump-probe anisotropy measurements and isotopic dilution clearly reveal that the decay of the dangling OH stretch excitation is almost entirely due to a jump to a hydrogen-bonded configuration that occurs in 1.61 ± 0.10 ps. This is more than twice as fast as the jump time from one hydrogen-bonded configuration to another in bulk H2O but about 50% slower than the reported out-of-plane reorientation at the air/water interface. In contrast, the intrinsic population lifetime of the dangling OH stretch in the absence of such jumps is found to be >10 ps. Molecular dynamics simulations of air/water and hexane/water interfaces reproduce the fast jump dynamics of interfacial dangling OH with calculated jump times of 1.4 and 1.7 ps for the air and hydrophobic interfaces, respectively. The simulations highlight that while the air/water and hydrophobic/water surfaces exhibit great structural similarities, a small stabilization of the OH groups by the hydrophobic interface produces the pronounced difference in the dynamics of dangling bonds.

Bi(111) thin film with insulating interior but metallic surfaces.

The electrical conductance of epitaxial Bi thin films grown on BaF(2)(111) by molecular beam epitaxy has been systematically investigated as a function of both film thickness (4-540 nm) and temperature (5-300 K). Unlike bulk Bi as a prototypical semimetal, the Bi thin films up to 90 nm are found to be insulating in the interior but metallic on the surface. This finding not only has unambiguously resolved the long-standing controversy about the existence of the semimetal-semiconductor transition in Bi thin films but also provided a straightforward interpretation for the perplexing temperature dependence of the resistivity of Bi thin films, which in turn might have some potential applications in spintronics.