Non-Markovian near-infrared Q branch of HCl diluted in liquid Ar.
Non-Markovian near-infrared Q branch of HCl diluted in liquid Ar.
复制标题
HCl 的非马尔可夫近红外 Q 分支稀释在液体 Ar 中。
DOI：
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发表时间：
2013
影响因子：
4.4
通讯作者：
Justo Pérez
中科院分区：
文献类型：
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作者：
A. Padilla;Justo Pérez
本文利用基于Kubo累积展开技术的非马尔可夫光谱理论，定性地研究了HCl在液态Ar中稀释后的红外Q分支。通过分子动力学技术计算了该谱理论中存在的各向异性相互作用的统计参数，并发现各向异性相关时间的值比先前通过拟合程序或微观细胞模型获得的值大得多（2倍）。这一事实是决定性的观察中心Q共振的理论谱带，这是缺乏在丰富的以往的研究进行了通常的理论基础上久保累积展开技术。虽然在这项工作中使用的理论只允许定性的Q分支的研究，我们可以用它来研究未知的Q共振的特性，这是很难获得的量子模拟技术最近发展。例如，在本研究中，我们发现Q分支基本上是由谱线干扰产生的非马尔可夫（或记忆）效应，其中PR干扰轮廓基本上决定Q分支谱形状。此外，我们还发现，Q共振主要是由前两个振动能级的第一转动态产生的，这些转动态受溶剂作用的影响更大。
By using a non-Markovian spectral theory based in the Kubo cumulant expansion technique, we have qualitatively studied the infrared Q branch observed in the fundamental absorption band of HCl diluted in liquid Ar. The statistical parameters of the anisotropic interaction present in this spectral theory were calculated by means of molecular dynamics techniques, and found that the values of the anisotropic correlation times are significantly greater (by a factor of two) than those previously obtained by fitting procedures or microscopic cell models. This fact is decisive for the observation in the theoretical spectral band of a central Q resonance which is absent in the abundant previous researches carried out with the usual theories based in Kubo cumulant expansion techniques. Although the theory used in this work only allows a qualitative study of the Q branch, we can employ it to study the unknown characteristics of the Q resonance which are difficult to obtain with the quantum simulation techniques recently developed. For example, in this study we have found that the Q branch is basically a non-Markovian (or memory) effect produced by the spectral line interferences, where the PR interferential profile basically determines the Q branch spectral shape. Furthermore, we have found that the Q resonance is principally generated by the first rotational states of the first two vibrational levels, those more affected by the action of the dissolvent.