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Comparisons of Dispersion Force Bounding Methods with Applications to Anisotropic Interactions

机译:色散力边界方法与各向异性相互作用应用的比较

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Comparisons and applications are made of the various procedures which have been devised recently for obtaining bounds to dispersion force coefficients. Particular attention is given to the methods based on approximate Gaussian quadratures and on Pade´ approximants, both of which require oscillator‐strength sum rule values for their implementation. The equivalence of the bounds obtained from the two procedures, when identical input information is employed, is demonstrated to all orders, and the improvements that can result from the introduction of additional information, in the form of experimental transition frequencies and other sum rules, is investigated in the course of numerical applications. Comparisons with alternative bounding methods, such as those based on variational principles and related inner projection techniques, show that these procedures, which can also employ sum rule values for their implementation, are similar to the Gaussian quadrature and Pade´ methods and provide identical results if the same input information is employed. There also exists a second class of procedures which provides bounding inter‐relations directly among the dispersion force coefficients, without reference to sum rule values, thus forming a useful complement to the former procedures. Numerical applications to molecular hydrogen, nitrogen, and oxygen, and the inert gases and alkali atoms, using both theoretical and semiempirical sum rule values, indicate that the bounding procedures can provide anisotropic dispersion force estimates of greater accuracy than those which can currently be extracted from rotational relaxation and related experiments. Comparison with more approximate methods for estimating the anisotropies in dispersion interactions, based on static polarizability anisotropies, serves to delineate the limits of accuracy of such approximations. The polarizability anisotropy approximation is found to provide overestimates in every case.
机译:对最近设计的各种程序进行了比较和应用,以获得色散力系数的界限。特别注意基于近似高斯正交和Pade'近似的方法,这两种方法都需要振荡器和强度和规则值来实现。当使用相同的输入信息时,从两个程序中获得的边界的等价性被证明为所有阶,并且在数值应用过程中研究了以实验跃迁频率和其他和规则的形式引入附加信息可能带来的改进。与其他边界方法(例如基于变分原理和相关内投影技术的方法)的比较表明,这些过程(也可以使用求和规则值来实现它们)类似于高斯正交和帕德方法,如果使用相同的输入信息,则提供相同的结果。还有第二类过程,它直接在色散力系数之间提供边界间关系,而不参考和规则值,从而形成对前一个过程的有用补充。使用理论和半经验和规则值对分子氢、氮和氧以及惰性气体和碱原子的数值应用表明,边界程序可以提供比目前从旋转弛豫和相关实验中提取的各向异性色散力估计更高的精度。与基于静态偏振各向异性估计色散相互作用中各向异性的近似方法进行比较,有助于描述这种近似的精度极限。发现偏振率各向异性近似在每种情况下都提供了高估。

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