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本文在第一性原理计算基础上结合非平衡格林函数方法, 研究了量子干涉效应对连接镍电极的二噻吩硼烷(dithienoborepin, DTB)分子结自旋输运性质的影响, 并通过氨基和硝基钝化实现了对二噻吩硼烷分子异构体(DTB-A和DTB-B)的区分. 结果表明, 原始的DTB-A和DTB-B分子结在费米能级两侧都有一个自旋向上透射峰和一个自旋向下透射峰, 且两个透射峰的能量位置和高度基本相同. 因此, 原始DTB-A和DTB-B分子结的自旋向上和自旋向下电流曲线基本重合, 不能被明显区分. 然而, 研究发现量子干涉效应能不同程度地增强氨基钝化DTB-A分子结费米能级两侧分子轨道的自旋极化输运能力, 并减弱氨基钝化DTB-B分子结费米能级两侧分子轨道的自旋极化输运能力. 此外, 研究还发现量子干涉效应可以显著提高硝基钝化DTB-B分子结费米能级两侧分子轨道的自旋极化输运能力, 同时减弱硝基钝化DTB-A分子结费米能级两侧分子轨道的自旋极化输运能力. 由于量子干涉效应对氨基和硝基钝化的DTB异构体分子结自旋输运能力有不同的调制作用, 因此可以通过测量氨基和硝基钝化分子结的自旋电流值来区分DTB分子的两种异构体.Previous research results show that the conductance difference in molecular junction caused by quantum interference (QI) effect is an important way to identify isomers or improve the recognition sensitivity. Recently, single-molecule conductance of two fully π-conjugated dithienoborepin (DTB) isomers (DTB-A and DTB-B) with tricoordinate boron centers has been measured by using the scanning tunneling microscopy break junction technique. The result shows that QI can enhance chemical responsivity in single-molecule DTB junction. In this work, the first-principles method based on density functional theory and non-equilibrium Green's function is used to study the influence of QI effect on spin-transport property of DTB molecular junction connected to the nickel electrode, and the purpose of distinguishing DTB isomers (DTB-A and DTB-B) is realized by using amino and nitro passivation. The results show that the pristine DTB-A molecule and DTB-B molecule both have a up-spin transmission peak dominated by HOMO and a down-spin transmission peak dominated by LUMO on both sides of the Fermi level, and the energy positions and coefficients of two transmission peaks are basically the same. Therefore, the up-spin and down-spin current curves of the two junctions basically coincide, so that it is impossible to clearly distinguish the two isomers of DTB molecule simply by spin current. The QI can enhance the spin-polarized transport capability of two orbitals of amino-passivated DTB-A molecule to varying degrees but weaken the spin-polarized transport capability of two orbitals of amino-passivated DTB-B molecule. Therefore, the current of DTB-A molecular junction passivated by amino group is always higher than that of DTB-B molecular junction passivated by amino group. However, the QI can greatly enhance the spin-polarized transport capability of two orbitals of nitro-passivated DTB-B molecule but weaken the spin-polarized transport capability of two orbitals of nitro-passivated DTB-A molecule. Therefore, the current of DTB-B molecular junction passivated by nitro is always higher than that of DTB-A molecular junction passivated by nitro. Because the QI has different effects on the spin-transport capability of DTB-A and DTB-B passivated by amino or nitro group, so the two isomers of DTB molecule can be distinguished by measuring the spin current value. The above conclusions provide more theoretical guidance for the practical preparation of spin molecular junctions and the regulation of their spin-transport performance in the future.
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Keywords:
- first principles /
- density functional theory /
- molecular device /
- quantum interference /
- spin-transport








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