Theoretical Investigation of the β Value of the π-Conjugated Molecular Wires by Evaluating Exchange Interaction between Organic Radicals
Theoretical Investigation of the β Value of the π-Conjugated Molecular Wires by Evaluating Exchange Interaction between Organic Radicals
复制标题
通过评估有机自由基之间的交换相互作用来理论研究 π 共轭分子线的 β 值
DOI：
10.1021/jp407452p
复制
发表时间：
2013
期刊：
影响因子：
3.7
通讯作者：
Kenji Matsuda
中科院分区：
文献类型：
--
作者：
Shohei Nishizawa;Jun-ya Hasegawa;Kenji Matsuda
π共轭分子线的衰减常数β对应于电子隧穿通过分子的效率。本文用密度泛函理论计算了有机双分子的分子内磁交换相互作用β值（硝酰基氮氧化物）具有几个分子线单元，即低聚对亚苯基（OPE）、低聚亚苯基亚乙炔基（OPE）、低聚亚苯基亚乙烯基（OPV）、低聚亚苯基亚胺（OPI）、双环[1.1.1]戊烷低聚物（BCP）、β，内消旋，β-三重稠合卟啉低聚物（TFP）和内消旋，meso-连接卟啉低聚物（MLP）。对于OPE、OPV、OPI、BCP、TFP和MLP，β计算值分别为0.41、0.25、0.22、0.32、0.77、0.03和0.65 <$-1。计算得到的β值与分子隧道电导的实验值吻合较好，表明交换作用与分子电导的机理相似.该方法可用于估算电子隧穿分子导线的效率。
The decay constant β of π-conjugated molecular wire corresponds to the efficiency of electron tunneling through the molecule. We have calculated β values of intramolecular magnetic exchange interactions by density functional theory for organic bis(nitronyl nitroxide)s that have several molecular wire units, namely, oligo-p-phenylene (OPP), oligophenylene ethynylene (OPE), oligophenylene vinylene (OPV), oligophenylene imine (OPI), bicyclo[1.1.1]pentane oligomer (BCP), β,meso,β-triply fused porphyrin oligomer (TFP), andmeso,meso-linked porphyrin oligomer (MLP). For OPP, OPE, OPV, OPI, BCP, TFP, and MLP, β was calculated to be 0.41, 0.25, 0.22, 0.32, 0.77, 0.03, and 0.65 Å–1, respectively. The obtained β values are in good agreement with the experimental value of the molecular tunneling conductance, suggesting similarity of the mechanism between exchange interaction and molecular conductance. This method can be used to estimate the efficiency of electron tunneling through the molecular wire.