Journal of Physical Chemistry B, Vol.119, No.21, 6448-6456, 2015
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 (nu(N=N) and nu(N=N)), carboxylic acid (nu(C=O)), and succinimide ester (nu(as)(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. The transport speed of 8.0 angstrom/ps was observed when initiated by either nu(C=O) or nu as(C=O). When initiated by nu(N=N) and nu(N=N), the transport speed of 14.4 +/- 2 and 11 +/- 4 angstrom/ps was observed. Analysis of the vibrational relaxation channels of different tags, combined with the results for the group velocity evaluation, permits identification of the chain bands predominantly contributing to the transport for different cases of the transport initiation. For the transport initiated by nu(N=N) the CH2 twisting and wagging chain bands were identified as the major energy transport channels. For the transport initiated by nu(C=O), the C-C stretching and CH2 rocking chain bands served as major energy transporters. The transport initiated by nu(N=N) results in direct formation of the wave packet within the CH2 twisting and wagging chain bands. These developments can aid in designing molecular systems featuring faster and more controllable energy transport in molecules.