Azofra Luis Miguel, Alkorta Ibon, Scheiner Steve
Instituto de Química Médica, CSIC, Juan de la Cierva 3, E-28006 Madrid, Spain.
Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300, USA.
J Chem Phys. 2014 Jun 28;140(24):244311. doi: 10.1063/1.4884962.
The (O3)2 dimer potential energy surface is thoroughly explored at the ab initio CCSD(T) computational level. Five minima are characterized with binding energies between 0.35 and 2.24 kcal/mol. The most stable may be characterized as slipped parallel, with the two O3 monomers situated in parallel planes. Partitioning of the interaction energy points to dispersion and exchange as the prime contributors to the stability, with varying contributions from electrostatic energy, which is repulsive in one case. Atoms in Molecules analysis of the wavefunction presents specific O⋯O bonding interactions, whose number is related to the overall stability of each dimer. All internal vibrational frequencies are shifted to the red by dimerization, particularly the antisymmetric stretching mode whose shift is as high as 111 cm(-1). In addition to the five minima, 11 higher-order stationary points are identified.
在从头算耦合簇单双激发（CCSD(T)）计算水平上对(O₃)₂二聚体的势能面进行了全面研究。确定了五个极小值，其结合能在0.35至2.24千卡/摩尔之间。最稳定的结构可描述为平行滑移结构，两个O₃单体位于平行平面内。相互作用能的分解表明，色散和交换是稳定性的主要贡献因素，静电能的贡献各不相同，在一种情况下是排斥性的。对波函数进行的分子中的原子分析显示了特定的O⋯O键相互作用，其数量与每个二聚体的整体稳定性有关。所有内部振动频率通过二聚化都向低频移动，特别是反对称拉伸模式，其移动高达111厘米⁻¹。除了这五个极小值外，还识别出11个高阶驻点。
