N2O+离子B2П态的光谱与光解离动力学

引用本文: 孙中发, 高治, 吴向坤, 唐国强, 周晓国, 刘世林. N₂O⁺离子B²П态的光谱与光解离动力学[J]. 物理化学学报, 2015, 31(5): 829-835. doi: 10.3866/PKU.WHXB201503041 shu

Citation: SUN Zhong-Fa, GAO Zhi, WU Xiang-Kun, TANG Guo-Qiang, ZHOU Xiao-Guo, LIU Shi-Lin. Excitation Spectra and Photodissociation Dynamics of the B²П State of the N₂O⁺ Ion[J]. Acta Physico-Chimica Sinica, 2015, 31(5): 829-835. doi: 10.3866/PKU.WHXB201503041 shu

N₂O⁺离子B²П态的光谱与光解离动力学

基金项目:
国家自然科学基金(21373194) (21373194)

国家重点基础研究发展规划项目(973) (2013CB834602)资助 (973) (2013CB834602)

摘要:

用一束波长为360.55 nm的激光直接作用于超声射流的N₂O分子束, 通过(3+1)共振增强多光子电离(REMPI)过程制备纯净的N₂O⁺(X²П(0,0,0))母体离子, 再用另一束波长在243-278 nm范围的激光将母体离子激发至B²П态后解离. 扫描解离激光波长, 监测NO⁺离子碎片的强度, 从而获得N₂O⁺离子B²П态的光致碎片激发(PHOFEX)谱. 通过拟合转动分辨光谱, 得到了相应的转动常数和自旋分裂常数, 从而区分了A²Σ⁺态高振动能级和B²П态带源的贡献, 明确了N₂O⁺离子B²П态的光谱"带头"位置(37154 cm^-1), 并将获得的振动光谱初步归属为B²П(v₁,v₂,v₃)←X²П的振动跃迁序列. 通过对NO⁺碎片离子的飞行时间质谱峰形的分析, 还获得了解离过程中释放的平均平动能, 并结合电子激发态势能面, 讨论了N₂O⁺离子B²П态的解离机理.

关键词:

English

Excitation Spectra and Photodissociation Dynamics of the B²П State of the N₂O⁺ Ion

1.
Hefei National Laboratory for Physical Sciences at Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China
Received Date: 05 January 2015
Available Online: 08 May 2015
Fund Project:
国家自然科学基金(21373194)

国家重点基础研究发展规划项目(973) (2013CB834602)资助

Abstract:

N₂O⁺ ions in the X²П(0,0,0) ground state were prepared by (3+1) resonance-enhanced multiphoton ionization (REMPI) of jet-cooled N₂O molecules at 360.55 nm, and then photoexcited to various vibrational levels in the B²П state over a wavelength range of 243-278 nm, followed by dissociation. The photofragment excitation (PHOFEX) spectrum was recorded by measuring the intensity of NO⁺ ion fragments vs excitation wavelength. The rotational constants and spin-orbit coupling were obtained by fitting the rotational structures of the vibrational bands. Thus, the contributions of highly excited vibronic levels of A²Σ⁺ states were distinguished from the other bands, and the original band of B²П state was verified. The series of vibrational bands in the PHOFEX spectrum were assigned to the transition of B²П(v₁,v₂,v₃) ←X²П. The average released kinetic energy of dissociation from the various B²П(v₁,v₂,v₃) ionic states was obtained by fitting the spreading contour of the NO⁺ ion peak in time-of-flight mass spectra. Dissociation mechanisms of N₂O⁺(B²П) were proposed with the aid of the theoretical potential energy surfaces of N₂O⁺ ions.

Key words:

N₂O⁺ ion
/ Resonance enhanced multiphoton ionization
/ Vibrational spectroscopy
/ Time-of-flight mass spectrum
/ Photodissociation

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沈阳化工大学材料科学与工程学院沈阳 110142

N₂O⁺离子B²П态的光谱与光解离动力学

English

Excitation Spectra and Photodissociation Dynamics of the B²П State of the N₂O⁺ Ion

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