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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Key Role of Deep Orbitals in the d(x2-y2)-d(3z2-r2) Gap in Tetragonal Complexes and 10Dq
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Key Role of Deep Orbitals in the d(x2-y2)-d(3z2-r2) Gap in Tetragonal Complexes and 10Dq

机译：深度轨道在四方复合物中D（X2-y2）-D（3Z2-R2）间隙中的深度轨道的关键作用和10DQ

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摘要

Using first-principles calculations, we show that the origin of the intrinsic a(1g)(similar to 3z(2) - r(2))-b(1g)(similar to x(2) - y(2)) splitting, Delta(int), in tetragonal transition-metal complexes and the variations of the cubic field splitting, 10Dq, with the metal-ligand distance, R, are much more subtle than commonly thought. As a main novelty, the key role played by covalent bonding with deep valence ligand levels and thus the inadequacy of too simple models often used for the present goal is stressed. Taking as a guide the isolated D-4h CUF64- complex, it is proved that Delta(int), essentially arises from bonding with deep 2s(F) orbitals despite them lying similar to 23 eV below 2p(F) orbitals. This conclusion, although surprising, is also supported by results on octahedral fluoride complexes where the contribution to 10Dq splitting from bonding with 2s(F) orbitals is behind its strong R dependence, stressing that explanations based on the crystal-field approach are simply meaningless.
机译：利用第一性原理计算，我们表明，在四方过渡金属配合物中，本征a（1g）（类似于3z（2）-r（2））-b（1g）（类似于x（2）-y（2））分裂δ（int）的起源，以及立方场分裂10Dq随金属-配体距离r的变化，比通常认为的要微妙得多。作为一个主要的新颖之处，强调了深价配体水平的共价键所起的关键作用，以及通常用于本目标的过于简单的模型的不足。以孤立的D-4h-CUF64-络合物为指导，证明了δ（int）本质上是由深2s（F）轨道的键合而产生的，尽管它们位于2p（F）轨道之下类似于23ev。这一结论虽然令人惊讶，但也得到了八面体氟化物配合物的结果的支持，其中2s（F）轨道成键对10Dq分裂的贡献是其强烈的R依赖性的背后，强调基于晶体场方法的解释毫无意义。

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