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Chemistry is about energy and its changes: A critique of bond-length/bond-strength correlations

机译：化学与能量及其变化有关：对键长/键强度相关性的批评

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摘要

The current usage of bond-length/bond-strength (BLBS) correlations, namely, that a shorter bond must be associated with larger dissociation energy and/or force constant, is appraised. The numerous exceptions to these rules are noted. The originators of these rules considered them as useful empirical correlations, but in the course of time these relationships have often been painted as laws. As shall be seen, each exception to these rules can be explained by some effects, like strain, steric effects, dispersion stabilization, hybridization defects, bond ionicity, orbital shrinkage, and so on. As such, when the number of special reasons that can be invoked for failures of the BLBS rules, is close to the number of the exceptions to these rules, one must conclude that such correlations cannot be considered as anything even close to physical laws. Indeed, it is often the exceptions to the rules that point to interesting bonding aspects and/or reorganization processes. We argue against disregarding bond dissociation energies or related energy quantities in this context. While the various reorganization processes involved in determining these energy quantities may complicate the BLBS correlations appreciably, compared to the properties that probe structures only close to equilibrium, their consideration cannot be avoided if we want to extract chemical sense from the notion of a bond strength. (C) 2017 Elsevier B.V. All rights reserved.
机译：评估了键长/键强度（BLBS）相关性的当前用法，即较短的键必须与较大的离解能和/或力常数相关联。注意这些规则的许多例外。这些规则的创建者认为它们是有用的经验相关性，但是随着时间的流逝，这些关系常常被描绘成定律。可以看出，这些规则的每个例外都可以用某些效应来解释，例如应变，空间效应，分散稳定性，杂交缺陷，键离子性，轨道收缩等。这样，当可以因BLBS规则的失败而被调用的特殊原因的数量接近于这些规则的例外的数量时，必须得出这样的结论：这些相关性不能被认为是任何近似于物理定律的事物。确实，规则的例外通常指向有趣的绑定方面和/或重组过程。我们反对在这种情况下忽略键解离能或相关能的数量。尽管确定这些能量数量所涉及的各种重组过程可能会使BLBS相关性复杂化，但与仅探测接近平衡的结构相比，如果我们想从结合强度的概念中提取化学意义，就不能避免考虑它们。 （C）2017 Elsevier B.V.保留所有权利。

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  • 来源
    《Coordination chemistry reviews》 |2017年第8期|355-362|共8页
  • 作者

    Kaupp Martin; Danovich David; Shaik Sason;

  • 作者单位

    Tech Univ Berlin, Inst Chem, Theoret Chem, Sekr C 7 Str 17 Juni,135, D-10623 Berlin, Germany;

    Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel|Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel;

    Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel|Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel;

  • 收录信息 美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    Badger's rule; Bond dissociation energy; Bond length; Chemical bond; Force constants;

    机译：ger定律键解离能键长化学键力常数;

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