Bond length and local energy density property connections for non-transition-metal oxide-bonded interactions.
Bond length and local energy density property connections for non-transition-metal oxide-bonded interactions.
复制标题
非过渡金属氧化物键相互作用的键长和局部能量密度属性连接。
DOI：
10.1021/jp062992m
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发表时间：
2006
期刊：
影响因子：
--
通讯作者：
D. Cox
中科院分区：
文献类型：
--
作者：
G. V. Gibbs;M. Spackman;D. Jayatilaka;K. Rosso;D. Cox
对于各种分子和地球材料，理论局部动能密度G（r（c））增加，局部势能密度V（r（c））减小，因为M-O键长（M =与O键合的第一和第二行金属原子）减小，电子密度rho（r（c））在键临界点r（c）处累积。尽管声称每个电子电荷的局部动能密度G（r（c））/rho（r（c））在小于1时将键合相互作用分类为共享相互作用，在大于1时将键合相互作用分类为闭壳层相互作用，但是发现随着局部电子能量密度H（r（c））= G（r（c））+ V（r（c））减小并且变得越来越负，该比率从0.5增加到2.5 Au。该比率似乎是给定M-O键合相互作用的特征的量度，比率越大，rho（r（c））的值越大，M原子的配位数越小，并且键合相互作用的共享越多。H（r（c））/rho（r（c））与G（r（c））/rho（r（c））散点图将M-O键合相互作用分类为具有每电子电荷的局部电子能量密度H（r（c））/rho（r（c））的域，其倾向于随着键合原子对的电负性差减小而减小。用梯度修正的电子气理论表达式和局域维里定理估算的G（r（c））和V（r（c））值与理论值符合得很好，特别是对于第二排M原子的键合相互作用.对于共享的C-O和N-O键合相互作用，该协议较差。
For a variety of molecules and earth materials, the theoretical local kinetic energy density, G(r(c)), increases and the local potential energy density, V(r(c)), decreases as the M-O bond lengths (M = first- and second-row metal atoms bonded to O) decrease and the electron density, rho(r(c)), accumulates at the bond critical points, r(c). Despite the claim that the local kinetic energy density per electronic charge, G(r(c))/rho(r(c)), classifies bonded interactions as shared interactions when less than unity and closed-shell when greater, the ratio was found to increase from 0.5 to 2.5 au as the local electronic energy density, H(r(c)) = G(r(c)) + V(r(c)), decreases and becomes progressively more negative. The ratio appears to be a measure of the character of a given M-O bonded interaction, the greater the ratio, the larger the value of rho(r(c)), the smaller the coordination number of the M atom and the more shared the bonded interaction. H(r(c))/rho(r(c)) versus G(r(c))/rho(r(c)) scatter diagrams categorize the M-O bonded interactions into domains with the local electronic energy density per electron charge, H(r(c))/rho(r(c)), tending to decrease as the electronegativity differences for the bonded pairs of atoms decrease. The values of G(r(c)) and V(r(c)), estimated with a gradient-corrected electron gas theory expression and the local virial theorem, are in good agreement with theoretical values, particularly for the bonded interactions involving second-row M atoms. The agreement is poorer for shared C-O and N-O bonded interactions.