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在34至109K之间,NO(X²Π)和O₂对NO A(²Σ⁺,v' = 0)的低温碰撞猝灭

Low-temperature collisional quenching of NO A(2)Σ(+)(v' = 0) by NO(X(2)Π) and O2 between 34 and 109 K.

作者信息

Sánchez-González R, Eveland W D, West N A, Mai C L N, Bowersox R D W, North S W

机构信息

Department of Chemistry, Texas A&M University, 3012 TAMU, College Station, Texas 77843, USA.

Department of Aerospace Engineering, Texas A&M University, 3141 TAMU, College Station, Texas 77843, USA.

出版信息

J Chem Phys. 2014 Aug 21;141(7):074313. doi: 10.1063/1.4892980.

Abstract

We present measurements of collisional fluorescence quenching cross sections of NO(A(2)Σ(+), v' = 0) by NO(X(2)Π) and O2 between 34 and 109 K using a pulsed converging-diverging nozzle gas expansion, extending the temperature range of previous measurements. The thermally averaged fluorescence quenching cross sections for both species show a monotonic increase as temperature decreases in this temperature range, consistent with earlier observations. These new measurements, however, allow discrimination between predictions obtained by extrapolating fits of previous data using different functional forms that show discrepancies exceeding 120% for NO and 160% for O2 at 34 K. The measured self-quenching cross section is 52.9 Å(2) near 112 K and increases to 64.1 Å(2) at 35 K, whereas the O2 fluorescence quenching cross section is 42.9 Å(2) at 109 K and increases to 58.3 Å(2) at 34 K. Global fits of the quenching cross section temperature dependence show that, when including our current measurements, the low temperature behavior of the quenching cross sections for NO and O2 is better described by a parameterization that accounts for the long-range interactions leading to the collisional deactivation via an inverse power law model.

摘要

我们利用脉冲式缩放喷嘴气体膨胀技术,给出了34至109 K之间NO(X²Π)和O₂对NO(A²Σ⁺, v' = 0)的碰撞荧光猝灭截面的测量结果,扩展了先前测量的温度范围。在该温度范围内,两种物质的热平均荧光猝灭截面均随温度降低呈单调增加,这与早期观测结果一致。然而,这些新的测量结果能够区分通过外推先前数据拟合得到的预测结果,这些拟合使用了不同的函数形式,在34 K时,对于NO,差异超过120%,对于O₂,差异超过160%。测量得到的自猝灭截面在112 K附近为52.9 Ų,在35 K时增加到64.1 Ų,而O₂的荧光猝灭截面在109 K时为42.9 Ų,在34 K时增加到58.3 Ų。猝灭截面温度依赖性的全局拟合表明,当纳入我们当前的测量结果时,通过考虑长程相互作用并通过逆幂律模型导致碰撞失活的参数化方法,可以更好地描述NO和O₂猝灭截面的低温行为。

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