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ArXe⁺的低电子态及其势能函数。

The low-lying electronic states of ArXe+ and their potential energy functions.

作者信息

Zehnder O, Merkt F

机构信息

Laboratorium für Physikalische Chemie, ETH Zurich, 8093 Zurich, Switzerland.

出版信息

J Chem Phys. 2008 Jan 7;128(1):014306. doi: 10.1063/1.2815801.

Abstract

Photoionization and pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectra of ArXe have been recorded between 96 400 and 108 200 cm(-1) following resonance-enhanced two-photon excitation via selected vibrational levels of the C 1 and D 0+ Rydberg states. The PFI-ZEKE photoelectron spectra consist of three vibrational progressions corresponding to the X 1/2<--X 0+, A1 3/2<--X 0+, and A2 1/2<--X 0+ transitions. From these progressions, adiabatic ionization energies, equilibrium internuclear distances, and vibrational constants have been derived for the lowest three electronic states of ArXe+. The photoionization spectra reveal long progressions of autoionizing Rydberg states converging to the lowest vibrational levels of the A1 3/2 state. A potential model has been developed that enables a global description of the low-lying electronic states of the heteronuclear rare gas dimer ions. The model explicitly treats the effects of the spin-orbit, charge-exchange, and long-range interactions. This model was used to obtain potential energy functions for all six low-lying electronic states of ArXe+ from the experimental positions of the vibrational levels of the X 1/2, A1 3/2, and A2 1/2 states relative to the ground neutral state and existing spectroscopic data on the B 1/2, C1 3/2, and C2 1/2 states.

摘要

通过C 1和D 0 +里德堡态的选定振动态进行共振增强双光子激发后,记录了ArXe在96400至108200 cm(-1)之间的光电离和脉冲场电离零动能(PFI-ZEKE)光电子能谱。PFI-ZEKE光电子能谱由对应于X 1/2<--X 0 +、A1 3/2<--X 0 +和A2 1/2<--X 0 +跃迁的三个振动序列组成。从这些序列中,推导出了ArXe +最低三个电子态的绝热电离能、平衡核间距和振动常数。光电离能谱揭示了自电离里德堡态向A1 3/2态最低振动态收敛的长序列。已经开发了一个势模型,能够对异核稀有气体二聚体离子的低电子态进行全局描述。该模型明确考虑了自旋轨道、电荷交换和长程相互作用的影响。利用该模型,根据X 1/2、A1 3/2和A2 1/2态相对于基态中性态的振动态实验位置以及关于B 1/2、C1 3/2和C2 1/2态的现有光谱数据,获得了ArXe +所有六个低电子态的势能函数。

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