Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on first row diatomic hydrides
Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on first row diatomic hydrides
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DOI：
10.1063/1.465307
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发表时间：
1993-08
影响因子：
4.4
通讯作者：
K. Peterson;R. Kendall;T. H. Dunning
中科院分区：
文献类型：
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作者：
K. Peterson;R. Kendall;T. H. Dunning
用单(HF+1+2)和多(GVB+1+2和CAS+1+2)参考内收缩单、双激发组态相互作用(CI)波函数计算了第一排双原子氢化物BH、CH、NH、OH和Hf的电子基态势能函数。对于每种方法，利用Dunning和同事的关联一致基组，研究了所导出的光谱常数和离解能相对于单粒子基组大小的系统增加的收敛。文中还讨论了用额外的漫反射函数来增强基集的效果。使用双(cc-pVDz)至五(cc-pV5Z)zeta质量集合，利用正则收敛行为，对每种理论方法的Ee、De、Re和ωe的完全基集(CBS)极限进行了估计。将估算的CBS限值与已有的实验结果进行了比较，并得出了与CBS限值相关的固有误差。
Potential energy functions have been calculated for the electronic ground states of the first row diatomic hydrides BH, CH, NH, OH, and HF using single‐ (HF+1+2) and multi‐ (GVB+1+2 and CAS+1+2) reference internally contracted single and double excitation configuration interaction (CI) wave functions. The convergence of the derived spectroscopic constants and dissociation energies with respect to systematic increases in the size of the one‐particle basis set has been investigated for each method using the correlation consistent basis sets of Dunning and co‐workers. The effect of augmenting the basis sets with extra diffuse functions has also been addressed. Using sets of double (cc‐pVDZ) through quintuple (cc‐pV5Z) zeta quality, the complete basis set (CBS) limits for Ee, De, re, and ωe have been estimated for each theoretical method by taking advantage of the regular convergence behavior. The estimated CBS limits are compared to the available experimental results, and the intrinsic errors associated with...