Leong Tammy X, Qasim Layla N, Mackin Robert T, Du Yuchen, Pascal Robert A, Rubtsov Igor V
Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA.
J Chem Phys. 2021 Apr 7;154(13):134304. doi: 10.1063/5.0046932.
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 8.6 km/s, which exceeds the speed of sound in common metals (∼5 km/s) and polymers (∼2 km/s). Efficiencies of energy injection into the chain and transport along the chain are found to be very high and dependent on the extent of conjugation across the structure. By tuning the degree of conjugation via electronic doping of the chain, the transport speed and efficiency can be controlled. The study opens avenues for developing materials with controllable energy transport properties for heat management, schemes with efficient energy delivery to hard-to-reach regions, including transport against thermal gradients, and ways for initiating chemical reactions remotely.
我们发现了一种利用聚对亚苯基链将高频振动量子在大距离上快速且单向地进行传输的方法。在对-COOH端基进行中红外光子光激发后,多余的能量被有效地注入到链中,形成沿链自由传播的振动波包。这种传输能传递高能振动量子,其传输速度范围可达8.6 km/s,超过了普通金属(约5 km/s)和聚合物(约2 km/s)中的声速。发现能量注入链和沿链传输的效率非常高,并且取决于整个结构的共轭程度。通过对链进行电子掺杂来调节共轭程度,可以控制传输速度和效率。该研究为开发具有可控能量传输特性的材料以进行热管理、为向难以到达的区域高效输送能量(包括逆热梯度传输)的方案以及远程引发化学反应的方法开辟了道路。