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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electronic structure and spectroscopy of oxyallyl: A theoretical study
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Electronic structure and spectroscopy of oxyallyl: A theoretical study

机译：羟基烯丙基的电子结构和光谱学：理论研究

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摘要

Electronic structure of the oxyallyl diradical and the anion is investigated using high-level ab initio methods. Converged theoretical estimates of the energy differences between low-lying electronic states of oxyallyl (OXA) as well as detachment energies of the anion are reported. Our best estimates of the adiabatic energy differences between the anion ~2A_2 and the neutral ~3B_2 and ~3B_1 states are 1.94 and 2.73 eV, respectively. The ~1A_1 state lies above ~3B_2 vertically, but geometric relaxation brings it below the triplet. The two-dimensional scan of the singlet ~1A _1 potential energy surface (PES) reveals that there is no minimum corresponding to a singlet diradical structure. Thus, singlet OXA undergoes prompt barrierless ring closure. However, a flat shape of the PES results in the resonance trapping in the Franck-Condon region, giving rise to the experimentally observable features in the photoelectron spectrum. By performing reduced-dimensionality wave packet calculations, we estimated that the wave packet lingers in the Franck-Condon region for about 170 fs, which corresponds to the spectral line broadening of about 200 cm~(-1). We also present calculations of the photodetachment spectrum and compare it with experimental data. Our calculations lend strong support to the assignment of the photoelectron spectrum of the OXA anion reported in Ichino et al. (Angew. Chem., Int. Ed. Engl. 2009, 48, 8509).
机译：使用高级从头算方法研究了羟基烯丙基双自由基和阴离子的电子结构。汇聚了对低位电子烯丙基（OXA）电子状态之间的能量差以及阴离子的脱离能的理论估计值。我们对阴离子〜2A_2与中性〜3B_2和〜3B_1状态之间绝热能差的最佳估计分别为1.94和2.73 eV。 〜1A_1状态垂直位于〜3B_2上方，但是几何弛豫将其置于三重态下方。单线态〜1A _1势能面（PES）的二维扫描显示，没有对应于单线态双自由基结构的最小值。因此，单线态OXA会迅速发生无障碍环闭合。然而，PES的平坦形状导致在弗朗克-康登区的共振陷获，从而在光电子光谱中产生了实验上可观察到的特征。通过进行降维波包计算，我们估计波包在Franck-Condon区域停留约170 fs，这对应于约200 cm〜（-1）的谱线展宽。我们还介绍了光解离光谱的计算，并将其与实验数据进行了比较。我们的计算为Ichino等人报道的OXA阴离子的光电子光谱分配提供了有力的支持。 （Angew.Chem。，Int.Ed.Engl.2009，48，8509）。

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