Unidirectional coherent energy transport via conjugated oligo(p-phenylene) chains.

We discovered a way to funnel high-frequency vibrational quanta rapidly and unidirectionally over large distances using oligo(p-phenylene) chains. After mid-IR photon photoexcitation of a -COOH end group, the excess energy is injected efficiently into the chain, forming vibrational wavepackets that propagate freely along the chain. The transport delivers high-energy vibrational quanta with a range of transport speeds reaching 8.

C-D Vibration at C2 Position of Imidazolium Cation as a Probe of the Ionic Liquid Microenvironment.

Unlike molecular solvents, imidazolium-based ionic liquids are entirely made of ions with spatial heterogeneity. There is a need for spectroscopic probes that can assess the microenvironment near the cations of these complex liquids. In this manuscript, we describe simple chemical procedures to label the C2 position of imidazolium cation with a C-D vibrational probe and show, through linear and nonlinear vibrational spectroscopies, that this C-D stretching mode can be a useful analytical tool to assess both the solvent microenvironment and solute-solvent interactions in imidazolium-based ionic liquids from the cation point of view.

Ballistic Energy Transport in Oligomers.

The development of nanocomposite materials with desired heat management properties, including nanowires, layered semiconductor structures, and self-assembled monolayer (SAM) junctions, attracts broad interest. Such materials often involve polymeric/oligomeric components and can feature high or low thermal conductivity, depending on their design. For example, in SAM junctions made of alkane chains sandwiched between metal layers, the thermal conductivity can be very low, whereas the fibers of ordered polyethylene chains feature high thermal conductivity, exceeding that of many pure metals.

Band-selective ballistic energy transport in alkane oligomers: toward controlling the transport speed.

Intramolecular transport of vibrational energy in two series of oligomers featuring alkane chains of various length was studied by relaxation-assisted two-dimensional infrared spectroscopy. The transport was initiated by exciting various end-group modes (tags) such as different modes of the azido (ν(N≡N) and ν(N═N)), carboxylic acid (ν(C═O)), and succinimide ester (νas(C═O)) with short mid-IR laser pulses. It is shown that the transport via alkane chains is ballistic and the transport speed is dependent on the type of the tag mode that initiates the transport.

Fully automated dual-frequency three-pulse-echo 2DIR spectrometer accessing spectral range from 800 to 4000 wavenumbers.

A novel dual-frequency two-dimensional infrared instrument is designed and built that permits three-pulse heterodyned echo measurements of any cross-peak within a spectral range from 800 to 4000 cm(-1) to be performed in a fully automated fashion. The superior sensitivity of the instrument is achieved by a combination of spectral interferometry, phase cycling, and closed-loop phase stabilization accurate to ~70 as. The anharmonicity of smaller than 10(-4) cm(-1) was recorded for strong carbonyl stretching modes using 800 laser shot accumulations.