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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Hidden Bond Anomalies: The Peculiar Case of the Fluorinated Amine Chalcogenides
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Hidden Bond Anomalies: The Peculiar Case of the Fluorinated Amine Chalcogenides

机译：隐藏的键异常：氟化胺硫属元素化物的特殊情况。

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摘要

Bond anomalies have been investigated for a set of 53 molecules with either N-F, Ti-P, Cr-H, Pb-C, or Pb-F bonds for which reverse rather than inverse bond length-bond strength relationships have been previously claimed. The intrinsic strength of each bond investigated was determined utilizing the associated local stretching force constant obtained at the CCSD(T)/aug-cc-pVTZ level of theory. For the metal containing molecules, LC-omega PBE calculations with the aug-cc-pVTZ (Cr, Pb) and the 6-31++G(d,p) basis set (Ti) were carried out. For bonds containing a metal atom, any bond anomaly could not be confirmed. Previously reported results were due to ill-defined bond strength descriptors or lacking accuracy. In the case of the fluoro amines, methyl fluoro amines, and the fluor amine oxides, direct or hidden bond anomalies were detected, which result from two or more opposing electronic effects: a dominant bond shortening effect due to electron withdrawal and a bond weakening due to lone pair repulsion or hybridization defects. Bond anomalies can be disguised by a complex interplay of electronic effects. These hidden bond anomalies could be identified in this work for the fluoro amine chalcogenides.
机译：已经研究了一组具有N-F，Ti-P，Cr-H，Pb-C或Pb-F键的53个分子的键异常，这些键先前已要求反向而非反向的键长-键强度关系。利用理论上的CCSD（T）/ aug-cc-pVTZ水平获得的相关局部拉伸力常数确定所研究的每个键的固有强度。对于含金属的分子，使用aug-cc-pVTZ（Cr，Pb）和6-31 ++ G（d，p）基组（Ti）进行LC-ωPBE计算。对于包含金属原子的键，无法确定任何键异常。先前报告的结果归因于结合强度描述符不明确或缺乏准确性。在氟代胺，甲基氟代胺和氟代胺氧化物的情况下，检测到直接或隐藏的键异常，这是由两个或多个相反的电子效应引起的：由于电子吸收引起的显着键缩短作用和由于键减弱引起的键减弱。孤对排斥或杂交缺陷。键异常可以通过电子效应的复杂相互作用来掩盖。在这项工作中，对于氟胺硫属元素化物可以发现这些隐藏的键异常。

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