当前位置: X-MOL 学术J. Mol. Spectrosc. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Evaluation of Expansion Coefficients from Optimal Fitting Parameters for the Analysis of Spectra of Diatomic Molecules and an Application to LiH
Journal of Molecular Spectroscopy ( IF 1.4 ) Pub Date : 2001-06-01 , DOI: 10.1006/jmsp.2001.8333
Hiromichi Uehara 1 , J. F. Ogilvie
Affiliation  

To evaluate individual expansion coefficients composing fitting parameters of the Born-Oppenheimer corrections to Dunham's coefficients Y(ij) that have been given analytically with the Delta(B) and Delta(omega) formalism, we examined the consistency of analytic expressions for those corrections with Watson's assertion of the experimental inseparability of nonadiabatic corrections Q(a, b)(r) for a molecule AB. Derived analytic expressions in terms of optimal fitting parameters for the corrections are essential to evaluate individual expansion coefficients. These expressions also reveal redundancies between empirical correction parameters Delta(ij). A method of evaluating nonadiabatic vibrational corrections Q(a, b)(r) and adiabatic corrections S(a, b)(r) separately consistent with Watson's assertion of inseparability is presented and is applied to an analysis of spectral data of LiH. Functions Q(a, b) and S(a, b) for LiH are thus successfully evaluated; S(H, Li)(r) values agree well with those predicted simply by wobble-stretch theory. Experimental values for optimal fitting parameters r(H)(1q) and r(H)(2q) are nearly equal to those of r(Li)(1q) and r(Li)(2q), respectively, in agreement with a theoretical relation r(a)(iq)=r(b)(iq). Copyright 2001 Academic Press.

中文翻译:

从用于分析双原子分子光谱的最佳拟合参数评估膨胀系数及其在 LiH 中的应用

为了评估构成对 Dunham 系数 Y(ij) 的 Born-Oppenheimer 校正的拟合参数的各个膨胀系数,这些系数已通过 Delta(B) 和 Delta(omega) 形式主义分析给出,我们检查了这些校正的解析表达式的一致性沃森关于分子 AB 的非绝热校正 Q(a, b)(r) 的实验不可分性的断言。就校正的最佳拟合参数而言,派生的解析表达式对于评估各个膨胀系数是必不可少的。这些表达式还揭示了经验校正参数 Delta(ij) 之间的冗余。一种评估非绝热振动修正 Q(a, b)(r) 和绝热修正 S(a, b)(r) 的方法,分别符合 Watson' 提出了不可分离性的断言,并将其应用于 LiH 光谱数据的分析。因此,成功评估了 LiH 的函数 Q(a, b) 和 S(a, b);S(H, Li)(r) 值与摆动拉伸理论简单预测的值非常吻合。最佳拟合参数 r(H)(1q) 和 r(H)(2q) 的实验值分别几乎等于 r(Li)(1q) 和 r(Li)(2q) 的实验值,与理论值一致关系 r(a)(iq)=r(b)(iq)。版权所有 2001 学术出版社。与理论关系 r(a)(iq)=r(b)(iq) 一致。版权所有 2001 学术出版社。与理论关系 r(a)(iq)=r(b)(iq) 一致。版权所有 2001 学术出版社。
更新日期:2001-06-01
down
wechat
bug