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首页> 外文期刊>Structural Chemistry >On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites
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On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites

机译：关于自旋和轨道分辨的Cu + -NO在气相和沸石中Cu（I）位转移的性质

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Electronic factors essential for NO activation by Cu(I) sites in zeolites are investigated within spin-resolved analysis of electron transfer channels (natural orbitals for chemical valence). NOCV analysis is performed for three DFT-optimized models of Cu(I)–NO site in ZSM-5: [CuNO]+, (T1)CuNO, and (M7)CuNO. NO as a non-innocent, open-shell ligand reveals significant differences between independent deformation density components for α and β spins. Four distinct components are identified: (i) unpaired electron donation from NO π‖* antibonding orbital to Cus,d; (ii) backdonation from copper d yz to π⊥* antibonding orbital; (iii) donation from occupied π‖ and Cu d xz to bonding region, and (iv) donation from nitrogen lone-pair to Cus,d. Channel (i), corresponding to one-electron bond, shows-up solely for spin majority and is effective only in the interaction of NO with naked Cu+. Channel (ii) dominates for models b and c: it strongly activates NO bond by populating antibonding π* orbital and weakens the N–O bond in contrast to channel (i), depopulating the antibonding orbital and strengthening N–O bond. This picture perfectly agrees with IR experiment: interaction with naked Cu+ imposes small blue-shift of NO stretching frequency while it becomes strongly red-shifted for Cu(I) site in ZSM-5 due to enhanced backdonation.
机译：在电子传递通道（化学价的自然轨道）的自旋分辨分析中，研究了沸石中Cu（I）部位激活NO所必需的电子因子。对ZSM-5中Cu（I）–NO位点的三个DFT优化模型进行了NOCV分析：[CuNO] + ，（T1）CuNO和（M7）CuNO。 NO作为非纯的开壳配体显示出α和β自旋的独立变形密度成分之间的显着差异。确定了四个不同的成分：（i）NOπ' *反键轨道对Cus，d 的不成对电子给予； （ii）从d yz 到π⊥ *反键轨道的回输； （iii）从被占据的π'和Cu d xz 向键合区域的捐赠，以及（iv）从氮孤对向Cus，d 的捐赠。通道（i）对应于一个电子键，仅以自旋占多数出现，并且仅在NO与裸Cu + 的相互作用中有效。通道（ii）在模型b和c中占主导地位：与通道（i）相比，它通过填充反键π*轨道强烈激活NO键，并弱化N-O键，从而使反键轨道减少并增强N-O键。这张图片与IR实验完全吻合：与裸Cu + 的相互作用强加了NO拉伸频率的小蓝移，而ZSM-5中的Cu（I）位则由于增强的背键作用而发生了强烈的红移。

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