Spatially resolved vibrational energy transfer in molecular monolayers.
We have shown that it is possible to input heat to one location of a molecule and simultaneously measure its arrival in real time at two other locations, using an ultrafast flash-thermal conductance technique. A femtosecond laser pulse heats an Au layer to approximately 800 degrees C, while vibrational sum-frequency generation spectroscopy (SFG) monitors heat flow into self-assembled monolayers (SAMs) of organic thiolates. Heat flow into the SAM creates thermally induced disorder, which decreases the coherent SFG signal from the CH-stretching transitions. Recent improvements in the technique are described, including the use of nonresonant background-suppressed SFG. The improved apparatus was characterized using alkanethiolate and benzenethiolate SAMs. In the asymmetric 2-methyl benzenethiolate SAM, SFG can simultaneously monitor CH-stretching transitions of both phenyl and methyl groups. The phenyl response to flash-heating occurs at least as fast as the 1 ps time for the Au surface to heat. The methyl response has a faster portion similar to the phenyl response and a slower portion characterized by an 8 ps time constant. The faster portions are attributed to disordering of the methyl-substituted phenyl rings due to thermal excitation of the Au-S adbonds. The slower portion, seen only in the methyl SFG signal, is attributed to heat flow from the metal surface into the phenyl rings and then to the methyl groups.
Carter
Jeffrey A
JA
School of Chemical Sciences, University of Illinois at Urbana-Champaign, Chemical and Life Sciences Laboratory, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.
Wang
Zhaohui
Z
Dlott
Dana D
DD
D002244:Carbon / Q000737:chemistry; D004735:Energy Transfer; D006358:Hot Temperature; D013057:Spectrum Analysis; D013997:Time Factors; D014732:Vibration
D002244:Carbon