烯丙基自由基CH2CHCH2的真空紫外激光脉冲场电离光电子研究。

Vacuum ultraviolet laser pulsed field ionization-photoelectron study of allyl radical CH2CHCH2.

作者信息

Xing Xi, Reed Beth, Lau Kai-Chung, Ng C Y, Zhang Xu, Ellison G Barney

机构信息

Department of Chemistry, University of California, Davis, Davis, California 95616.

出版信息

J Chem Phys. 2007 May 7;126(17):171101. doi: 10.1063/1.2737443.

DOI:10.1063/1.2737443

PMID:17492849

Abstract

The pulsed field ionization-photoelectron (PFI-PE) spectrum of allyl radical CH2CHCH2 (C3H5) in the energy range of 65 200-66 600 cm-1 has been measured using vacuum ultraviolet laser. Based on the simulation of the rotational structures resolved in the vibrational PFI-PE bands of C3H5+(X 1A1;0(0+) and nu7+=1), the ionization energies (IEs) of C3H5(X 2A2;0(0)) to form C3H5+(X 1A1;0(0+) and nu7+=1) are determined to be 65 584.6+/-2.0 cm-1 (8.131 46+/-0.000 25 eV) and 66 020.9+/-2.0 cm-1 (8.185 56+/-0.000 25 eV), respectively, where nu7+(a1) is the symmetric C-C-C bending mode of C3H5+(X 1A1). These values are compared to IE(C3H5) values obtained in previous experimental and high-level ab initio quantum theoretical studies.

摘要

使用真空紫外激光测量了烯丙基自由基CH2CHCH2（C3H5）在65200 - 66600 cm-1能量范围内的脉冲场电离光电子（PFI - PE）光谱。基于对C3H5 +（X 1A1；0（0 +）和ν7 + = 1）振动PFI - PE带中分辨出的转动结构的模拟，确定了C3H5（X 2A2；0（0））形成C3H5 +（X 1A1；0（0 +）和ν7 + = 1）的电离能（IEs）分别为65584.6±2.0 cm-1（8.13146±0.00025 eV）和66020.9±2.0 cm-1（8.18556±0.00025 eV），其中ν7 +（a1）是C3H5 +（X 1A1）的对称C - C - C弯曲模式。将这些值与先前实验和高水平从头算量子理论研究中获得的IE（C3H5）值进行了比较。