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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Fluorescence Excitation and Emission Spectroscopy of the X 1A′ f A 1A′′ System of CHI and CDI
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Fluorescence Excitation and Emission Spectroscopy of the X 1A′ f A 1A′′ System of CHI and CDI

机译：CHI和CDI的X 1A'f A 1A''系统的荧光激发和发射光谱

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We report on the first detailed studies of the spectroscopy of an iodocarbene, measuring fluorescence excitation and emission spectra of theX 1A′ fA 1A′′ system of :CHI and the deuterated isotopomer :CDI. Due to similar bending and C-I stretching frequencies in the upper state, fluorescence excitation spectra of :CHI show polyads composed of members of the 20 n-x30 x progressions with x ) 0-3. For :CDI, only progressions with x ) 0, 1 are observed. Extrapolation of the 20 n term energies for both isotopomers to a common origin places the electronic origin of the X 1A′ f A 1A′′ system near 10 500 cm-1, in good agreement with theoretical predictions. Rotational analysis of the 16 observed bands for CHI and 13 observed bands for :CDI yields rotational constants for the upper and lower states that are also in good agreement with theory. To investigate the controversial issue of the ground state multiplicity of :CHI, we measured single vibronic level emission spectra from many A 1A′′ levels. These spectra show conclusively that the ground state is a singlet, as for both isotopomers the a3A′′ origin is observed, lying well above the origin of the A 1A′ state. At energies above the a3A′′ origin, the spin-orbit mixing is so severe that few vibrational assignments can be made. Analysis of the emission spectra provides a lower limit on the singlet-triplet gap of 4.1 kcal mol-1, in excellent agreement with theoretical predictions.
机译：我们报告了碘碳烯的光谱的第一个详细研究，测量了：CHI和氘代异位异构体：CDI的X 1A'fA 1A''系统的荧光激发和发射光谱。由于在较高状态下类似的弯曲和C-1拉伸频率，：CHI的荧光激发光谱显示了由20 n-x30 x级数（x）0-3的成员组成的多单元组。对于：CDI，仅观察到x）0，1的进程。将两种同位素的20 n项能量外推到一个共同的原点，将X 1A'f A 1A''系统的电子原点置于10 500 cm-1附近，这与理论预测非常吻合。对CHI的16个观察带和：CDI的13个观察带进行旋转分析，得出上下状态的旋转常数，这也与理论相吻合。为了研究：CHI的基态多重性的有争议问题，我们从许多A 1A'水平测量了单个振动电子水平的发射光谱。这些光谱结论性地表明，基态是单重态，因为对于两种同位异构体，都观察到了a3A''的起源，远高于A 1A'态的起源。在a3A''原点以上的能量处，自旋轨道混合非常严重，几乎无法进行振动分配。发射光谱的分析提供了4.1 kcal mol-1的单重态-三重态间隙的下限，与理论预测非常吻合。

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