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[从RbH(X 1σ⁺,v = 0 - 2)的振动能级到H₂的振动能量转移]

[Vibrational energy transfer from vibrational levels of RbH(X 1sigma+, v = 0-2) to H2].

作者信息

Shen Xiao-Yan, Wang Shu-Ying, Liu Jing, Dai Kang, Shen Yi-Fan

机构信息

School of Chemistry and Molecular Engineering, East China University of Science & Technology, Shanghai 200237, China.

出版信息

Guang Pu Xue Yu Guang Pu Fen Xi. 2011 Jan;31(1):39-42.

Abstract

The vibrational energy transfer from vibrational levels of RbH(X 1sigma+, v = 0-2) by collision with H2 was determined using the integrated time-resolved laser induced fluorescence (LIF) in a five-arm crossed heat-pipe oven. Rb-H2 mixture was irradiated with pulses of 696.4 nm radiation from a OPO laser, populating 6D state by two-photon absorption. The vibrational levels of RbH(X 1sigma+) generated in the reaction of Rb(6D) and H2 were detected by LIF technique. The nascent quantum state distributions of RbH were obtained when the delay time between the pump and probe laser was 20 ns. The nascent RbH product molecules were found to populate the lowest three vibrational (v = 0, 1, 2) levels of the ground electronic state but could not be detected in any higher vibrational state. The integrated time-resolved LIF excited A 1sigma+ --> X 1sigma+ system in the presence of H2 was recorded with delay time from 0 to 10 micros. The RbH signal of v = 0, 1 levels first increased and then decreased on a larger time scale. RbH was created instantaneously then was quenched by collision and diffused. The rate equations for the population of the vibrational levels were given. The integrated profiles method permitted us to determine the rate coefficients for vibrational transfer of RbH(X 1sigma+, v = 0-2) by collision with H2. The rate coefficients for collisional transfer of RbH(X 1sigma+) by collisions with H2 are (in units of 10-(11) cm3 x s(-1)) 3.4 +/- 0.8 and 2.8 +/- 0.6 for v = 2 --> v = 1 and v = 1 --> v = 0 respectively. The diffusion rates of v = 0, 1, 2 are (in units of 10(5) s(-1)) 4.9 +/- 1.1, 1.0 +/- 0.3 and 0.6 +/- 10.2, respectively. The experiment showed that vibrational relaxation from RbH(X 1sigma+, v = 0-2) was more efficient compared to that of other vibrational levels studied here.

摘要

在五臂交叉热管炉中,通过积分时间分辨激光诱导荧光(LIF)技术,测定了RbH(X 1σ⁺,v = 0 - 2)振动态与H₂碰撞时的振动能量转移。用光学参量振荡器(OPO)激光的696.4 nm辐射脉冲照射Rb - H₂混合物,通过双光子吸收使原子跃迁到6D态。利用LIF技术检测Rb(6D)与H₂反应生成的RbH(X 1σ⁺)的振动态。当泵浦激光和探测激光之间的延迟时间为20 ns时,获得了RbH的初始量子态分布。发现初始的RbH产物分子占据基电子态的最低三个振动(v = 0, 1, 2)能级,但在任何更高的振动态中都无法检测到。在有H₂存在的情况下,记录了积分时间分辨LIF激发的A 1σ⁺→X 1σ⁺系统,延迟时间从t = 0到10 μs。v = 0、1能级的RbH信号在较大时间尺度上先增加后减小。RbH瞬间产生,然后通过碰撞猝灭并扩散。给出了振动态布居的速率方程。积分轮廓法使我们能够确定RbH(X 1σ⁺,v = 0 - 2)与H₂碰撞时振动转移的速率系数。RbH(X 1σ⁺)与H₂碰撞转移的速率系数(单位:10⁻¹¹ cm³·s⁻¹),v = 2→v = 1时为3.4 ± 0.8,v = 1→v = 0时为2.8 ± 0.6。v = 0、1、2的扩散速率(单位:10⁵ s⁻¹)分别为4.9 ± 1.1、1.0 ± 0.3和0.6 ± 10.2。实验表明,与这里研究的其他振动态相比,RbH(X 1σ⁺,v = 0 - 2)的振动弛豫更有效。

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