Fantuzzi Felipe, Nascimento Marco Antonio Chaer
Instituto de Química, Universidade Federal do Rio de Janeiro , Rio de Janeiro, RJ 21941-909, Brazil.
J Chem Theory Comput. 2014 Jun 10;10(6):2322-32. doi: 10.1021/ct500334f.
The Generalized Product Function Energy Partitioning (GPF-EP) method has been applied to a set of molecules, AH (A = Li, Be, B, C, N, O, F), CO and LiF with quite different dipole moments, in order to investigate the role played by the quantum interference effect in the formation of polar chemical bonds. The calculations were carried out with GPF wave functions treating all the core electrons as a single Hartree-Fock group and the bonding electrons at the Generalized Valence Bond Perfect-Pairing (GVB-PP) level, with the cc-pVTZ basis set. The results of the energy partitioning into interference and quasi-classical contributions along the respective Potential Energy Surfaces (PES) show that the main contribution to the depth of the potential wells comes from the interference term, which is an indication that all the molecules mentioned above form typical covalent bonds. In all cases, the stabilization promoted by the interference term comes from the kinetic contribution, in agreement with previous results. The analysis of the effect of quantum interference on the electron density reveals that while polarization effects (quasi-classical) tend to displace electronic density from the most polarizable atom toward the less polarizable one, interference (quantum effects) counteracts by displacing electronic density to the bond region, giving rise to the right electronic density and dipole moment.
广义乘积函数能量划分（GPF-EP）方法已应用于一组具有相当不同偶极矩的分子AH（A = Li、Be、B、C、N、O、F）、CO和LiF，以研究量子干涉效应在极性化学键形成中所起的作用。计算是使用GPF波函数进行的，将所有内层电子视为一个单哈特里-福克组，并在广义价键完美配对（GVB-PP）水平处理成键电子，采用cc-pVTZ基组。沿着各自的势能面（PES）将能量划分为干涉和准经典贡献的结果表明，势阱深度的主要贡献来自干涉项，这表明上述所有分子都形成典型的共价键。在所有情况下，干涉项促进的稳定化来自动力学贡献，这与先前的结果一致。对量子干涉对电子密度的影响的分析表明，虽然极化效应（准经典）倾向于将电子密度从极化率最高的原子转移到极化率较低的原子，但干涉（量子效应）通过将电子密度转移到键区域来抵消这种影响，从而产生正确的电子密度和偶极矩。
