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H2 对 HDO 和 D2O 的转动激发:实验和理论微分截面。

Rotational excitation of HDO and D2O by H2: experimental and theoretical differential cross-sections.

机构信息

Institute for Molecules and Materials, Radboud University Nijmegen, Nijmegen, The Netherlands.

出版信息

J Chem Phys. 2013 Jan 14;138(2):024314. doi: 10.1063/1.4772600.

Abstract

We present state-to-state differential cross sections (DCSs) for rotationally inelastic scattering of HDO by normal- and para-H(2) at collision energies of 580 cm(-1) and 440 cm(-1). (2+1) resonance enhanced multiphoton ionization is used to detect rotationally cold HDO molecules before collision and as scattering products, which occupy higher rotational states due to collision with H(2). Relative integral cross sections of HDO are obtained by integrating its DCSs measured at the same experimental conditions. Experimental and theoretical DCSs of HDO scattered by normal- and para-H(2) are in good agreement in 30°-180° range of scattering angles. This partial agreement shows the accuracy of the recently tested potential of H(2)O-H(2), but now by using a completely different set of rotational transitions that are (unlike in H(2)O), not forbidden by nuclear spin restrictions. Similar results are presented for D(2)O scattered by normal-H(2) at collision energy of 584 cm(-1). The agreement between experiment and theory is, however, less good for forward scattering of HDO/D(2)O. A critical analysis of this discrepancy is presented.

摘要

我们呈现了 HDO 与正常和仲 H2 在碰撞能为 580 cm-1 和 440 cm-1 时的转动非弹性散射的态态微分截面(DCS)。(2+1)共振增强多光子电离被用于在碰撞前探测转动冷 HDO 分子,并作为散射产物,由于与 H2 的碰撞,它们占据了更高的转动态。通过在相同实验条件下测量 HDO 的 DCS,获得了 HDO 的相对积分截面。在散射角为 30°-180°的范围内,正常和仲 H2 散射的 HDO 的实验和理论 DCS 吻合良好。这种部分吻合表明了最近测试的 H2O-H2 势能的准确性,但现在使用的是一组完全不同的转动跃迁,这些跃迁(与 H2O 不同)不受核自旋限制的禁止。类似的结果也呈现了正常-H2 散射的 D2O 在碰撞能为 584 cm-1 时的 DCS。然而,对于 HDO/D2O 的前向散射,实验和理论之间的吻合度较差。对这种差异进行了批判性分析。

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