Highs and Lows of Bond Lengths: Is There Any Limit?
Highs and Lows of Bond Lengths: Is There Any Limit?
复制标题
DOI：
10.1002/anie.202102967
复制
发表时间：
2021-07-26
期刊：
影响因子：
--
通讯作者：
Baonza VG
中科院分区：
文献类型：
--
作者：
Lobato A;Salvadó MA;Recio JM;Taravillo M;Baonza VG
势能曲线（PEC）上的两个不同的点，零能量交叉点和拉伸力常数消失的点，使我们能够预测双原子，分子部分和晶体系统中两个原子之间可能的距离范围。我们证明了这些键稳定性边界是明确定义的，并且与基于电子密度的标量场的拓扑描述符相关，并且可以使用通用PECs计算。化学数据库和量子力学计算被用来分析来自s - p主块的一整套原子双原子键。重点放在了C - C共价键中取代基的影响上，结论是短于1.14 Å或长于2.0 Å的距离不太可能实现，这分别与超高压数据和过渡态距离一致。假定的例外用于将我们的模型置于正确的框架中，并制定链式相互作用的猜想，这为数百种化学系统报告的O−H距离的多模态直方图提供了解释。不能随意压缩或拉长化学键。两个键长保持器通过施加不能超过的限制来监视化学键的稳定性。在短距离内，硬球边界阻止相互作用变为正极。在长距离上，旋轴条件阻止了键力常数为负。两者都是平衡状态下键长的内在结果。
Two distinct points on the potential energy curve (PEC) of a pairwise interaction, the zero‐energy crossing point and the point where the stretching force constant vanishes, allow us to anticipate the range of possible distances between two atoms in diatomic, molecular moieties and crystalline systems. We show that these bond‐stability boundaries are unambiguously defined and correlate with topological descriptors of electron‐density‐based scalar fields, and can be calculated using generic PECs. Chemical databases and quantum‐mechanical calculations are used to analyze a full set of diatomic bonds of atoms from the s‐p main block. Emphasis is placed on the effect of substituents in C−C covalent bonds, concluding that distances shorter than 1.14 Å or longer than 2.0 Å are unlikely to be achieved, in agreement with ultra‐high‐pressure data and transition‐state distances, respectively. Presumed exceptions are used to place our model in the correct framework and to formulate a conjecture for chained interactions, which offers an explanation for the multimodal histogram of O−H distances reported for hundreds of chemical systems. Bonds cannot be compressed or elongated at will. Two bond‐length keepers watch for the stability of chemical bonds by imposing limits that cannot be exceeded. At short distances, the hard‐sphere boundary prevents the interaction from becoming positive. At long distances, the spinodal condition prevents the bond force constant to be negative. Both are intrinsic consequences of the bond length at equilibrium.
登录
查看更多内容
影响因子：
3.3
作者：
Contreras-Garcia, J.;Martin Pendas, A.;Recio, J. M.
通讯作者：
Recio, J. M.
比氢和氦重的两个原子之间最短键的成键分析：O22
影响因子：
2.9
作者：
Fu, Mingxing;Pan, Sudip;Frenking, Gernot
通讯作者：
Frenking, Gernot
影响因子：
4.3
作者：
Gaggioli, Carlo Alberto;Belpassi, Leonardo;Belanzoni, Paola
通讯作者：
Belanzoni, Paola
影响因子：
4.4
作者：
Beyer, MK
通讯作者：
Beyer, MK
影响因子：
4.4
作者：
Espinosa, E;Molins, E
通讯作者：
Molins, E