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首页> 外文期刊>RSC Advances >Thermally accessible triplet state of pi-nucleophiles does exist. Evidence from first principles study of ethylene interaction with copper species
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Thermally accessible triplet state of pi-nucleophiles does exist. Evidence from first principles study of ethylene interaction with copper species

机译：π-亲核试剂的热可及三重态确实存在。乙烯与铜物种相互作用的第一性原理研究的证据

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Three different models of ethylene interaction with copper species, namely, the Cu(100) surface, odd-numbered copper clusters C2H4/Cu-n (where n = 3, 7, 11, 15, 17, 19, 21, 25 and 27) and atomic copper C2H4/Cu were studied theoretically. It was found that the ethylene molecule possesses three different types of bonding depending on the presence of the unpaired spin on the reacting copper atom. These bonding structures demonstrate different types of band gap (bulk) or SOMO-LUMO gaps (cluster/atom), where SOMO stands for the singly occupied and LUMO means the lowest unoccupied molecular orbitals of the copper species. The obtained results are in good agreement with the previous experimental and computational results on the structural, spectral and energetic properties of the studied species. The bulk copper and sub-nanosized clusters (n > 7) build up the mono-pi-bonded ground state complexes with ethylene where the latter species possesses the C-2v symmetry. The single-atom complex C2H4/Cu forms the CS-symmetrical ground state (X) over tilde (2)A' and the excited B-2(2) and B-4 state complexes of the C-2v and C-2 symmetry, respectively. The (X) over tilde (2)A' state complex is mono-sigma-bonded and involves the singlet ethylene moiety. The more tightly bound excited B-2(2) complex has the di-sigma-bonded structure and corresponds to the triplet ethylene. The adiabatic energy difference between the B-2(2) and (X) over tilde (2)A' states is equal to 10.8 kcal mol(-1) and can be ascribed to the singlet-triplet splitting of the ethylene moiety interacting with copper. The QTAIM analysis supports the coordination type of the Cu-C bonds in all the studied complexes. Formation of the C2H4/Cu(100), C2H4/Cu-n and C2H4/Cu species is in accord with the well-known Dewar-Chatt-Duncanson model, in such a way that the opposing sigma-donation step yields the ground state complex ((X) over tilde (2)A'), while the subsequent more expensive supporting pi*-back donation step provides the excited B-2(2) state complex. In the present paper we have developed a computational procedure to optimize the latter complex.
机译：乙烯与铜物质相互作用的三种不同模型，即Cu（100）表面，奇数个铜簇C2H4 / Cu-n（其中n = 3、7、11、15、17、19、21、25和27 ）和原子铜C2H4 / Cu进行了理论研究。发现乙烯分子具有三种不同类型的键，这取决于反应的铜原子上未成对的自旋的存在。这些键合结构显示出不同类型的带隙（本体）或SOMO-LUMO间隙（簇/原子），其中SOMO表示单占据的空间，LUMO表示铜物种中最低的未占据分子轨道。所获得的结果与先前关于所研究物种的结构，光谱和能量特性的实验和计算结果高度吻合。大量的铜和亚纳米簇（n> 7）与乙烯建立了单π键结合的基态配合物，其中后者具有C-2v对称性。单原子络合物C2H4 / Cu在波浪号（2）A'上形成CS对称的基态（X），并以C-2v和C-2对称性激发B-2（2）和B-4态的激发态， 分别。代字号（2）A'上的（X）状态络合物是单σ键结合的，并涉及单线态乙烯部分。结合更紧密的激发B-2（2）配合物具有di-sigma-bonded结构，并对应于三重态乙烯。在波浪号（2）A'的状态下B-2（2）和（X）之间的绝热能差等于10.8 kcal mol（-1），可以归因于与之相互作用的乙烯部分的单重态-三重态分裂铜。 QTAIM分析支持所有研究的配合物中Cu-C键的配位类型。 C2H4 / Cu（100），C2H4 / Cu-n和C2H4 / Cu物种的形成符合众所周知的Dewar-Chatt-Duncanson模型，以使相反的sigma-donation步骤产生基态的方式复合体（在波浪号（2）A'上的（X），而随后更昂贵的支持pi * -back捐赠步骤提供了激发的B-2（2）状态复合体。在本文中，我们开发了一种计算程序来优化后者。

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