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NH2(Ã2A1)的辐射寿命随(0, 8, 0)和(0, 9, 0)振动带的转动能级的变化。

Variation of radiative lifetimes of NH2(Ã2A1) with rotational levels in the (0, 8, 0) and (0, 9, 0) vibration bands.

机构信息

Department of Chemistry, Howard University, Washington, District of Columbia 20059, USA.

出版信息

J Chem Phys. 2012 Jan 21;136(3):034307. doi: 10.1063/1.3676782.

Abstract

Radiative lifetimes from the first electronically excited state of the amidogen free radical, NH(2)(Ã(2)A(1)), are reported for rotational states in selected vibrational levels ν(2)' using laser-induced fluorescence. Thermal collision of argon, Ar(∗)((3)P(0), (3)P(2)) metastable atoms in a microwave discharge-flow system with ammonia (NH(3)) molecules produced ground state NH(2)(X̃(2)B(1)). The radiative lifetimes for the deactivation of NH(2)(Ã(2)A(1)) were determined by measuring the decay profiles of NH(2)(Ã(2)A(1) → X̃(2)B(1)). In addition to the Fermi resonances with the ground state that lengthen the radiative lifetimes, a systematic increase in the radiative lifetimes with rotational quantum number was observed. Furthermore, the average radiative lifetimes of the (0, 9, 0) Γ, τ(1) = 18.65 ± 0.47 μs and (0, 8, 0) Φ, τ(2) = 23.72 ± 0.65 μs levels were much longer than those of the (0, 9, 0) Σ, τ(3) = 10.62 ± 0.47 μs, and (0, 8, 0) Π, τ(4) = 13.55 ± 0.55 μs states suggesting increased mixing of the first electronic excited and the ground states.

摘要

报道了 amidogen 自由基 NH(2)(Ã(2)A(1))的第一电子激发态的辐射寿命,使用激光诱导荧光研究了选定振动能级 ν(2)’中转动态的辐射寿命。在微波放电流动系统中,氩气 (Ar(∗)((3)P(0), (3)P(2))亚稳原子与氨 (NH(3))分子发生热碰撞,生成基态 NH(2)(X̃(2)B(1))。通过测量 NH(2)(Ã(2)A(1) → X̃(2)B(1))的衰减曲线,确定了 NH(2)(Ã(2)A(1))的去活化辐射寿命。除了与基态的 Fermi 共振会延长辐射寿命外,还观察到辐射寿命随转动量子数的系统增加。此外,(0, 9, 0) Γ,τ(1) = 18.65 ± 0.47 μs 和 (0, 8, 0) Φ,τ(2) = 23.72 ± 0.65 μs 能级的平均辐射寿命远长于 (0, 9, 0) Σ,τ(3) = 10.62 ± 0.47 μs,和 (0, 8, 0) Π,τ(4) = 13.55 ± 0.55 μs 状态,表明第一电子激发态和基态之间的混合增加。

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