气液界面处的量子态分辨反应动力学：F(2P) 与角鲨烷反应中 HF(v,J) 产物的直接吸收检测

Quantum-state resolved reaction dynamics at the gas-liquid interface: direct absorption detection of HF(v,J) product from F(2P)+squalane.

作者信息

Zolot Alexander M, Harper Warren W, Perkins Bradford G, Dagdigian Paul J, Nesbitt David J

机构信息

JILA, National Institute of Standards and Technology, University of Colorado, Boulder, CO 80309, USA.

出版信息

J Chem Phys. 2006 Jul 14;125(2):21101. doi: 10.1063/1.2217016.

DOI:10.1063/1.2217016

PMID:16848566

Abstract

Exothermic reactive scattering of F atoms at the gas-liquid interface of a liquid hydrocarbon (squalane) surface has been studied under single collision conditions by shot noise limited high-resolution infrared absorption on the nascent HF(v,J) product. The nascent HF(v,J) vibrational distributions are inverted, indicating insufficient time for complete vibrational energy transfer into the surface liquid. The HF(v=2,J) rotational distributions are well fit with a two temperature Boltzmann analysis, with a near room temperature component (T(TD) approximately equal to 290 K) and a second much hotter scattering component (T(HDS) approximately equal to 1040 K). These data provide quantum state level support for microscopic branching in the atom abstraction dynamics corresponding to escape of nascent HF from the liquid surface on time scales both slow and fast with respect to rotational relaxation.

摘要

在单碰撞条件下，通过对新生HF（v，J）产物进行散粒噪声限制的高分辨率红外吸收，研究了液态烃（角鲨烷）表面气液界面处F原子的放热反应散射。新生HF（v，J）的振动分布是反转的，这表明没有足够的时间将振动能量完全转移到表面液体中。HF（v = 2，J）的转动分布通过双温度玻尔兹曼分析得到了很好的拟合，其中一个接近室温的组分（T（TD）约等于290 K）和第二个温度高得多的散射组分（T（HDS）约等于1040 K）。这些数据为原子提取动力学中的微观分支提供了量子态水平的支持，该微观分支对应于新生HF在相对于转动弛豫而言慢和快的时间尺度上从液体表面逸出。