Lee Mina, Kim Myung Soo
National Creative Research Initiative Center for Control of Reaction Dynamics and School of Chemistry, Seoul National University, Seoul 151-742, Korea.
J Phys Chem A. 2006 Aug 3;110(30):9377-82. doi: 10.1021/jp062456u.
Vibrational spectrum of vinyl chloride cation in the first excited electronic state, A2 A', was obtained by one-photon mass-analyzed threshold ionization (MATI) spectroscopy. Use of an improved vacuum ultraviolet radiation source based on four-wave sum frequency mixing in Hg resulted in excellent sensitivity for the MATI signals. From the MATI spectrum, the ionization energy to the A2 A' state of the cation was determined to be 11.6667 +/- 0.0006 eV. Nearly complete vibrational assignment for the MATI peaks was possible by utilizing the vibrational frequencies and Franck-Condon factors calculated at the DFT and TDDFT/B3LYP levels with the 6-311++G(3df,3pd) basis set. Geometry of the cation in the A2 A' state was determined by Franck-Condon fitting of the MATI spectrum.
通过单光子质量分析阈值电离（MATI）光谱法获得了处于第一激发电子态A2 A'的氯乙烯阳离子的振动光谱。使用基于汞中四波和频混合的改进型真空紫外辐射源，使得MATI信号具有出色的灵敏度。从MATI光谱中，确定阳离子到A2 A'态的电离能为11.6667 +/- 0.0006电子伏特。利用在DFT和TDDFT/B3LYP水平上使用6-311++G(3df,3pd)基组计算得到的振动频率和弗兰克-康登因子，几乎可以完成对MATI峰的完整振动归属。通过对MATI光谱进行弗兰克-康登拟合，确定了A2 A'态阳离子的几何结构。
