Institut des Sciences Moléculaires, Université de Bordeaux, CNRS UMR 5255, 33405 Talence Cedex, France.
J Chem Phys. 2011 Jul 28;135(4):044312. doi: 10.1063/1.3614502.
We present an application of the recently developed explicitly correlated coupled cluster method to the generation of the three-dimensional potential energy surface (PES) of the Ar-NO(+) cationic complex. A good overall agreement is found with the standard coupled clusters techniques employing correlation consistent atomic basis sets (aug-cc-pVnZ, n= D, T, Q) of Wright et al. This PES is then used in quantum close-coupling scattering and variational calculations to treat the nuclear motions. The bound states energies of the Ar-NO(+) complex obtained by both approaches are in good agreement with the available experimental results. The analysis of the vibrational wavefunctions shows strong anharmonic resonances between the low frequency modes (intermonomer bending and stretching modes) and the wavefunctions exhibit large amplitude motions.
我们展示了最近开发的显式关联耦合簇方法在生成 Ar-NO(+)阳离子配合物的三维势能面 (PES) 方面的应用。与 Wright 等人采用关联一致原子基组 (aug-cc-pVnZ，n=D，T，Q) 的标准耦合簇技术相比，我们发现了很好的整体一致性。然后，该 PES 用于量子密耦散射和变分计算来处理核运动。通过这两种方法获得的 Ar-NO(+)配合物的束缚态能量与可用的实验结果吻合较好。振动波函数的分析表明，低频模式（单体间弯曲和伸缩模式）之间存在强烈的非谐共振，并且波函数表现出大振幅运动。
