Full-dimensional quantum dynamics calculations of H(2)-H(2) collisions.
Full-dimensional quantum dynamics calculations of H(2)-H(2) collisions.
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DOI：
10.1063/1.3511699
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发表时间：
2011-01
期刊：
影响因子：
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通讯作者：
N. Balakrishnan;G. Quéméner;R. C. Forrey;R. Hinde;P. Stancil
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文献类型：
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作者：
N. Balakrishnan;G. Quéméner;R. C. Forrey;R. Hinde;P. Stancil
我们报道了两个准H(2)分子在碰撞能量范围内从超冷极限到热能的转动和振动能量转移的量子动力学计算。使用Hinde最近开发的全维H(2)-H(2)势能面(PES)得到的结果[J.化学]。太棒了。128,154308(2008年)]，与从Boothroyd，Martin，Keogh和Peterson(BMKP)PES得到的结果进行了比较[J.太棒了。116,666(2002)]。对于H(2)(v=1，j=0)与H(2)(v=0，j=0)碰撞的振动弛豫以及基态H(2)分子碰撞中的转动激发，Hinde的电子能谱得到的结果与已有的实验数据吻合较好。一种高效的近共振能量传递机制，它守恒内部转动角动量，并在我们之前对H(2)-H(2)系统的研究中发现[Phys。A 77,030704(R)(2008年)]欣德环境保护计划也复制了使用BMKP环境保护措施的环境保护措施，这表明这一过程在很大程度上对环境保护措施的细节不敏感。在没有近共振机制的情况下，振动弛豫是由势能面的各向异性驱动的。基于使用Hinde和BMKP PES获得的结果与可用的实验数据的比较，似乎Hinde PES提供了对H(2)-H(2)碰撞中的转动和振动跃迁的更准确的描述，至少对于振动量子数v≤1是这样。
We report quantum dynamics calculations of rotational and vibrational energy transfer in collisions between two para-H(2) molecules over collision energies spanning from the ultracold limit to thermal energies. Results obtained using a recent full-dimensional H(2)-H(2) potential energy surface (PES) developed by Hinde [J. Chem. Phys. 128, 154308 (2008)] are compared with those derived from the Boothroyd, Martin, Keogh, and Peterson (BMKP) PES [J. Chem. Phys. 116, 666 (2002)]. For vibrational relaxation of H(2)(v=1,j=0) by collisions with H(2)(v=0,j=0) as well as rotational excitations in collisions between ground state H(2) molecules, the PES of Hinde is found to yield results in better agreement with available experimental data. A highly efficient near-resonant energy transfer mechanism that conserves internal rotational angular momentum and was identified in our previous study of the H(2)-H(2) system [Phys. Rev. A 77, 030704(R) (2008)] using the BMKP PES is also found to be reproduced by the Hinde PES, demonstrating that the process is largely insensitive to the details of the PES. In the absence of the near-resonance mechanism, vibrational relaxation is driven by the anisotropy of the potential energy surface. Based on a comparison of results obtained using the Hinde and BMKP PESs with available experimental data, it appears that the Hinde PES provides a more accurate description of rotational and vibrational transitions in H(2)-H(2) collisions, at least for vibrational quantum numbers v ≤ 1.