Excited and ionic states of formamide: An excited-state photoelectron spectroscopy and ab initio study
Excited and ionic states of formamide: An excited-state photoelectron spectroscopy and ab initio study
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甲酰胺的激发态和离子态：激发态光电子能谱和从头算研究
DOI：
10.1063/1.1513456
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发表时间：
2002
影响因子：
4.4
通讯作者：
F. Zerbetto
中科院分区：
文献类型：
--
作者：
D. Steege;C. Lagrost;W. Buma;D. Leigh;F. Zerbetto
利用高分辨率激发态光电子能谱分析了双光子和三光子激发的甲酰胺激发态的光谱和动力学性质。结合从头算，这种方法已经导致了以前观察到的状态的各种重新分配，并观察到新的状态。本研究特别突出的一个方面是振动耦合的重要作用，它导致了高度混合的状态。然而，离子流形上的投影——正如我们在研究中所做的那样——能够确定波函数的各种贡献。我们的研究也使我们能够解决关于自由基阳离子基态和第一激发态电离能值的明显分歧。绝热值分别为10.233±0.008 eV和10.725±0.020 eV。我们的研究揭示的最后一个问题与地面的振动特性有关。
High-resolution excited-state photoelectron spectroscopy has been applied to unravel the spectroscopic and dynamic properties of the excited states of formamide populated by two- and three-photon excitation. In combination with ab initio calculations, this approach has led to various reassignments of previously observed states, and to the observation of new states. One of the aspects that particularly emerges from the present study is the important role of vibronic coupling, which leads to states of heavily mixed character. Projection on the ionic manifold—as is done in our studies—is, however, able to determine the various contributions of the wave function. Our studies have enabled us as well to resolve an apparent disagreement concerning the values of the ionization energies of the ground and first excited state of the radical cation. We find here adiabatic values of 10.233±0.008 and 10.725±0.020 eV, respectively. A final issue our studies shed light on concerns the vibrational properties of the ground...