Dynamics of Functionalized Surface Molecular Monolayers Studied with Ultrafast Infrared Vibrational Spectroscopy.

The structural dynamics of thin films consisting of tricarbonyl (1,10-phenanthroline)rhenium chloride (RePhen(CO)(3)Cl) linked to an alkyl silane monolayer through a triazole linker synthesized on silica-on-calcium-fluoride substrates are investigated using ultrafast infrared (IR) techniques. Ultrafast 2D IR vibrational echo experiments and polarization selective heterodyne detected transient grating (HDTG) measurements, as well as polarization dependent FT-IR and AFM experiments are employed to study the samples. The vibrational echo experiments measure spectral diffusion, while the HDTG experiments measure the vibrational excited state population relaxation and investigate the vibrational transition dipole orientational anisotropy decay. To investigate the anticipated impact of vibrational excitation transfer, which can be caused by the high concentration of RePhen(CO)(3)Cl in the monolayer, a concentration dependence of the spectral diffusion is measured. To generate a range of concentrations, mixed monolayers consisting of both hydrogen terminated and triazole/RePhen(CO)(3)Cl terminated alkyl silanes are synthesized. It is found that the measured rate of spectral diffusion is independent of concentration, with all samples showing spectral diffusion of 37 ± 6 ps. To definitively test for vibrational excitation transfer, polarization selective HDTG experiments are conducted. Excitation transfer will cause anisotropy decay. Polarization resolved heterodyne detected transient grating spectroscopy is sensitive to anisotropy decay (depolarization) caused by excitation transfer and molecular reorientation. The HDTG experiments show no evidence of anisotropy decay on the appropriate time scale, demonstrating the absence of excitation transfer the RePhen(CO)(3)Cl. Therefore the influence of excitation transfer on spectral diffusion is inconsequential in these samples, and the vibrational echo measurements of spectral diffusion report solely on structural dynamics. A small amount of very fast (~2 ps time scale) anisotropy decay is observed. The decay is concentration independent, and is assigned to wobbling-in-a-cone orientational motions of the RePhen(CO)(3)Cl. Theoretical calculations reported previously for experiments on a single concentration of the same type of sample suggested the presence of some vibrational excitation transfer and excitation transfer induced spectral diffusion. Possible reasons for the experimentally observed lack of excitation transfer in these high concentration samples are discussed.