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^7LiH分子基态及若干激发态的平衡几何及垂直激发能的从头算

ISSN号：1000-0364
期刊名称：《原子与分子物理学报》
时间：0
分类：O613.11[理学—无机化学;理学—化学]
作者机构：[1]信阳师范大学物理电子工程学院,信阳464000, [2]河南师范大学物理与信息工程学院,新乡453007
相关基金：国家自然科学基金（10574039）

关键词：从头算, 平衡几何, 垂直激发能, ^7LiH分子, ab initio calculation, equilibrium geometry, vertical excitation energy, ^7LiH molecule

中文摘要：

使用“对称性匹配簇-组态相互作用方法”（SAC／SAC—CI），在多种基组下计算了^7LiH分子X^1∑^＋、A^1∑^＋、B^1Ⅱ及b^3Ⅱ态的平衡几何，并将由“几何优化”得到的相应各态的平衡几何与“单点能扫描”得到的结果进行了比较。比较的结果表明，由“几何优化”得到的相应各态的平衡几何，与“单点能扫描”得到的结果存在着差异。分析的结果表明，在完全活性空间中，由“SAC／SAC-CI”方法进行“单点能扫描”得到的结果，比“几何优化”得到的结果更加合理。首次报告了使用6-311G（3df，3pd）基组进行“单点等扫描”得到的相应各态的平衡几何。其值分别是：基态（X^1∑^＋）为0．1588nm、单重态的第一激发态（A^1∑^＋）为0．2487nm、单重态的第二激发态（B^1Ⅱ）为0．2434nm、三重态的第二激发态（b^3Ⅱ）为0．1958nm。这一计算结果与实验值非常接近。还研究了从基态到上述相应各态的垂直激发能，在基态的平衡位置处，其值分别为（A^1∑^＋←X^1∑^＋）3．613eV、（B^1Ⅱ←X^1∑^＋）4．612ev和（b^3Ⅱ-X^1∑^＋）4．233eV。与其它理论计算结果进行比较后得出，本文的计算结果非常接近于使用很复杂的计算方法获得的结果。

英文摘要：

The comparison between single-point energy scanning（ SPES） and geometry optimization（OPT）in determining the equilibrium geometry of ^7LiH molecule is made at numerous basis sets using a symmetry-adapted-duster/symmetry-adapted-duster configuration-interaction（SAC/SAG-CI）method.The difference of the results obtained by SPES and by OPT is reported. The conclusion is gained that the results obtained by SPES are from reasonable than those obtained by OPT in the SAC/SAC-CI calculations in full active space. The accurate equilibrium geometries of the X^1∑^＋, A^1∑^＋ ,B^1Ⅱ and b^3Ⅱ states are firstly calculated using the SAC/SAC-CI method at 6-311G（3df,3pd）basis set,and are of 0. 1588 nm for the X^1∑^＋ state,0. 2487 nm for the A^1∑^＋ state,0.2434nm for the B^1Ⅱ state and 0. 1958nm for the b^3Ⅱ state, respectively. The vertical excitation energies from the ground to A^1∑^＋ ,B^1Ⅱ and b^3Ⅱ states are calculated,and are of 3.613 eV for the A^1∑^＋ state,4. 612 eV for the B^1Ⅱ state and 4.233 eV for the b^3Ⅱ state at the ground-state equilibrium separation,respectively. Comparison of the theoretical calculations of equilibrium internuclear separations for these states with those obtained by previous theories dearly show that the present work is in excellent agreement with experimental data. And the vertical excitation energies from the ground to these excited states are much close to those attained by very complicated methods.

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