Departamento de Química, Universidade de Coimbra, 3004-535 Coimbra, Portugal.
J Phys Chem A. 2012 May 10;116(18):4646-56. doi: 10.1021/jp302173h. Epub 2012 Apr 27.
A global accurate double-many-body expansion potential-energy surface is reported for the electronic ground state of N(2)O. The new form is shown to accurately mimic the ab-initio points calculated at the multireference configuration interaction level using the aug-cc-pVTZ basis set and the full-valence-complete-active-space wave function as reference. To improve the calculated raw energies, they have been extrapolated to the completed basis set limit and most importantly to the full configuration-interaction limit by correcting semiempirically the calculated dynamical correlation with the double-many-body expansion-scaled external correlation method. The topographical features of the novel potential-energy surface were examined in detail and compared with those of other potential functions available in the literature. Good agreement with the experimental data is observed.
报道了 N(2)O 电子基态的全局精确双多体展开势能面。新形式准确地模拟了使用 aug-cc-pVTZ 基组和全价完整活性空间波函数作为参考的多参考组态相互作用水平计算的从头算点。为了提高计算的原始能量，已将其外推至完全基组极限，最重要的是通过用双多体展开-扩展外部相关方法校正计算的动态相关来外推至完整组态相互作用极限。详细检查了新势能面的地形特征，并与文献中其他可用的势能函数进行了比较。观察到与实验数据的良好一致性。
