在固体氖中分离出的乙烯基自由基的红外吸收光谱。

Infrared absorption spectra of vinyl radicals isolated in solid Ne.

作者信息

Wu Yu-Jong, Lin Meng-Yeh, Cheng Bing-Ming, Chen Hui-Fen, Lee Yuan-Pern

机构信息

National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan.

出版信息

J Chem Phys. 2008 May 28;128(20):204509. doi: 10.1063/1.2929826.

DOI:10.1063/1.2929826

PMID:18513034

Abstract

Irradiation of samples of solid Ne near 3.0 K containing ethene (C(2)H(4)) with vacuum ultraviolet radiation at 120 nm from synchrotron yielded new spectral lines at 3141.0, 2953.6, 2911.5, 1357.4, 677.1, 895.3, and 857.0 cm(-1). These features are assigned to alpha-CH stretching (nu(1)), CH(2) antisymmetric stretching (nu(2)), CH(2) symmetric stretching (nu(3)), CH(2)-bending (nu(5)), HCCH cis bending (nu(7)), CH(2) out-of-plane bending (nu(8)), and alpha-CH out-of-plane bending (nu(9)) modes of C(2)H(3), respectively, based on results of (13)C- and D-isotopic experiments and quantum-chemical calculations. These calculations using density-functional theory (B3LYP and PW91PW91/aug-cc-pVTZ) predict vibrational wavenumbers, IR intensities, and isotopic ratios of vinyl radical that agree satisfactorily with our experimental results.

摘要

用来自同步加速器的120纳米真空紫外辐射照射含有乙烯（C₂H₄）的3.0 K附近的固态氖样品，在3141.0、2953.6、2911.5、1357.4、677.1、895.3和857.0厘米⁻¹处产生了新的谱线。基于¹³C和D同位素实验以及量子化学计算的结果，这些特征分别被归属为C₂H₃的α-CH伸缩振动（ν₁）、CH₂反对称伸缩振动（ν₂）、CH₂对称伸缩振动（ν₃）、CH₂弯曲振动（ν₅）、HCCH顺式弯曲振动（ν₇）、CH₂面外弯曲振动（ν₈）和α-CH面外弯曲振动（ν₉）模式。使用密度泛函理论（B3LYP和PW91PW91/aug-cc-pVTZ）进行的这些计算预测了乙烯基自由基的振动波数、红外强度和同位素比率，与我们的实验结果令人满意地相符。