Analysis of Low-Lying Gerade Rydberg States of Acetylene Using Two-Photon Resonance Fluorescence Excitation Spectroscopy

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• 作者：Kazuhide Tsuji ; Kentaro Misawa ; Junichi Awamura ; Akio Kawai ; Kazuhiko Shibuya
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：February 21, 2013
• 年：2013
• 卷：117
• 期：7
• 页码：1420-1427
• 全文大小：357K
• 年卷期：v.117,no.7(February 21, 2013)
• ISSN：1520-5215

文摘

The np gerade Rydberg states of acetylene were analyzed using two-photon resonance fluorescence excitation spectroscopy in the 72鈥?00鈥?3鈥?00 cm^鈥? energy region. The np蟺¹危_g⁺ and np蟺¹螖_g Rydberg series (n = 3鈥?) were identified in the fluorescence excitation spectrum measured by monitoring the C₂ d³螤_g鈥揳³螤_u Swan system. Some vibronic bands were assigned to the np蟺¹螖_g鈥揦̃¹危_g⁺ transition on the basis of rotational analysis. The 5p蟽¹螤_g state was observed, which is the first such observation in an np蟽¹螤_g series. Rotational analysis of the 5p蟽¹螤_g鈥揦̃¹危_g⁺ transition showed e/f-symmetry dependent predissociation of acetylene in the 5p蟽¹螤_g state. The 0₀⁰ band of the deuterated acetylene (C₂D₂) 4p蟺¹危_g⁺鈥揦̃¹危_g⁺ transition exhibits an atypical structure, which was satisfactorily reproduced by a simple model of quantum interference between the discrete and quasi-continuum states. The predissociative lifetimes of the np蟺gerade Rydberg states were estimated from the spectral profiles. The predissociation mechanism of acetylene in the Rydberg states is discussed.