School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom.
J Chem Phys. 2012 Jun 28;136(24):244313. doi: 10.1063/1.4730302.
The interaction of nitric oxide (NO) in its ground state X(2)Π and the first excited Rydberg state A(2)Σ(+) with an argon (Ar) atom has been studied using density functional theory. A number of exchange-correlation functionals that account for dispersion interactions have been considered, including functionals with both empirical and non-empirical treatments of dispersion. To study NO in the excited state, the recently developed maximum overlap method was used. Potential energy surfaces for interaction of NO with Ar have been constructed and parameters describing their minima, such as NO-Ar distance, orientation angle, and binding energy, have been determined. A comparison with combined experimental and accurate theoretical data has been made in terms of these parameters and the overall shape of the surfaces. For the ground state, several of the functionals give very good results. Treatment of the excited state is more problematic. None of the functionals considered provides completely satisfactory results. Several reasons for this failure have been identified: an incorrect description of the non-dispersion component of the interaction and the damping of the dispersion interaction at small interatomic distances.
采用密度泛函理论研究了一氧化氮（NO）在基态 X(2)Π 和第一激发态 Rydberg 态 A(2)Σ(+)与氩（Ar）原子的相互作用。考虑了许多考虑色散相互作用的交换关联泛函，包括具有经验和非经验色散处理的泛函。为了研究激发态中的 NO，使用了最近开发的最大重叠方法。构建了 NO 与 Ar 相互作用的势能面，并确定了描述其最小值的参数，例如 NO-Ar 距离、取向角和结合能。根据这些参数和表面的整体形状，与组合实验和精确理论数据进行了比较。对于基态，几种泛函给出了非常好的结果。处理激发态的问题更多。所考虑的泛函都没有给出完全令人满意的结果。已经确定了这种失败的几个原因：相互作用的非分散分量的描述不正确以及在小原子距离处的分散相互作用的阻尼。
