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The Renner-Teller effect in HCCCN+(X̃2Π) studied by zero-kinetic energy photoelectron spectroscopy and theoretical calculations
The Journal of Chemical Physics ( IF 3.1 ) Pub Date : 2015-08-04 14:59:58 , DOI: 10.1063/1.4927005 Zuyang Dai 1 , Wei Sun 1 , Jia Wang 1 , Yuxiang Mo 1
The Journal of Chemical Physics ( IF 3.1 ) Pub Date : 2015-08-04 14:59:58 , DOI: 10.1063/1.4927005 Zuyang Dai 1 , Wei Sun 1 , Jia Wang 1 , Yuxiang Mo 1
Affiliation
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The spin-vibronic energy levels of the cyanoacetylene cation have been measured using the one-photon zero-kinetic energy (ZEKE) photoelectron spectroscopic method. All three degenerate vibrational modes showing vibronic coupling, i.e., Renner-Teller (RT) effect, have been observed. All the splitting spin-vibronic energy levels of the fundamental H—C≡C bending vibration (v 5) have been determined. The spin-vibronic energy levels of the degenerate vibrational modes have also been calculated using a diabatic model in which the harmonic terms as well as all the second-order vibronic coupling terms are used. The theoretical predictions are in good agreement with the experimental data and are used to assign the ZEKE spectrum. It is found that the RT effects for the H—(CC)—CN bending (v 7) and the C—C≡N bending (v 6) vibrations are weak, whereas they are strong for the H—C≡C bending (v 5) vibration. The cross-mode RT couplings between any of the two degenerate vibrations are strong. The spin-orbit resolved fundamental vibrational energy levels of the C≡N stretching (v 2) and C—H stretching (v 1) vibrations have also been observed. The spin-orbit energy splitting of the ground state has been determined for the first time as 43 ± 2 cm−1, and the ionization energy of HCCCN is found to be 93 903.5 ± 2 cm−1.
中文翻译：
零动能光电子能谱研究HCCCN +（X̃2Π）中的Renner-Teller效应及理论计算
氰基乙炔阳离子的自旋振动能级已使用单光子零动能（ZEKE）光电子能谱法进行了测量。观察到了所有三个简并的振动模式，显示出振动耦合，即Renner-Teller（RT）效应。确定了基本HCC弯曲振动（v 5）的所有分裂自旋振动能级。还使用绝热模型计算了简并振动模式的自旋振动能级，其中使用了谐波项以及所有二阶振动耦合项。理论预测与实验数据非常吻合，并用于分配ZEKE光谱。发现H-（CC）-CN弯曲的RT效应（v 7）和C–C≡N弯曲（v 6）振动较弱，而对于H–C≡C弯曲（v 5）振动则较强。两种简并振动中的任意一种之间的交叉模式RT耦合都很牢固。还观察到自旋轨道解析的C≡N拉伸（v 2）和CH拉伸（v 1）振动的基本振动能级。首次将基态的自旋轨道能量分裂确定为43±2 cm -1，并且发现HCCCN的电离能为93 903.5±2 cm -1。
更新日期：2015-08-05
中文翻译：
零动能光电子能谱研究HCCCN +（X̃2Π）中的Renner-Teller效应及理论计算
氰基乙炔阳离子的自旋振动能级已使用单光子零动能（ZEKE）光电子能谱法进行了测量。观察到了所有三个简并的振动模式，显示出振动耦合，即Renner-Teller（RT）效应。确定了基本HCC弯曲振动（v 5）的所有分裂自旋振动能级。还使用绝热模型计算了简并振动模式的自旋振动能级，其中使用了谐波项以及所有二阶振动耦合项。理论预测与实验数据非常吻合，并用于分配ZEKE光谱。发现H-（CC）-CN弯曲的RT效应（v 7）和C–C≡N弯曲（v 6）振动较弱，而对于H–C≡C弯曲（v 5）振动则较强。两种简并振动中的任意一种之间的交叉模式RT耦合都很牢固。还观察到自旋轨道解析的C≡N拉伸（v 2）和CH拉伸（v 1）振动的基本振动能级。首次将基态的自旋轨道能量分裂确定为43±2 cm -1，并且发现HCCCN的电离能为93 903.5±2 cm -1。
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