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Theoretical Study of Haloacetonitrile Anions: CH2XCN- (X=F, Cl)
Xin-wen Zhang,Mei Li,Shan-xi Tian¤
Author NameAffiliationE-mail
Xin-wen Zhang Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, China  
Mei Li Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Shan-xi Tian¤ Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, China; Department of Chemical Physics, University of Science and Technology of China, Hefei 230026,China sxtian@ustc.edu.cn 
Abstract:
Haloacetonitrile anions CH2XCN- (X=F, Cl) were studied by HF-SCF, Becke3-LYP, and MP2 methods together with the Dunning's basis set aug-cc-PVTZ. The vertical electron attachments to the neutral are endothermic. The geometrically optimized CH2FCN- is mainly a valence-bounded anion and CH2FCN-→CH2CN+F- is a nonadiabatic dissociation. This theoretical study in good agreement with the experimental results shows that the Becke3-LYP method is reasonable in describing the electronic structures of anions and dissociative attachment dynamics, while significant differences between MP2 and Becke3-LYP results are shown for the dissociation potential curves of CH2ClCN-→CH2CN+Cl-.2,70-(Ethylene)-bis-8-hydroxyquinoline was optimized with DFT/B3LYP and ab initio HF methods, so ionization potential and electron affinity could be determined. Absorption spectrum was calculated by ZINDO and TD-DFT. CIS method was used to calculate the S1 excited states of the compound and afterwards the emission spectrum was computed. When the solvent effect was taken into account, the computed results show encouraging agreement with known experimental data. The results of analyzing the relationship between the energies and absorption spectra indicate that the ability to transporting electrons is strengthened compared with 8-hydroxyquinoline and that absorption and emission spectra are red-shifted. The intramolecular reorganization energy of tris(2,70-(ethylene)-bis-8-hydroxyquinoline)-aluminum implies its electron transporting property is worse than tris(8-hydroxyquinoline)-aluminum. The predicted maximum emission wavelength is red-shifted compared with tris(8-hydroxyquinoline)-aluminum.
Key words:  Haloacetonitrile, Electron attachment, Dissociation dynamics, Electron correlation effect
FundProject:其它
Theoretical Study of Haloacetonitrile Anions: CH2XCN- (X=F, Cl)
张新文,李梅,田善喜¤
摘要:
使用HF-SCF、Becke3-LYP和MP2理论方法和Dunnning基组aug-cc-PVTZ对卤代乙腈负离子CH2XCN-(X=F,Cl)进行一系列计算. 计算说明电子垂直贴附到中性分子是吸热反应. 构型优化的负离子CH2FCN-主要是价层束缚类型,CH2FCN-→CH2CN+F-是非绝热解离过程. 在描述负离子的电子结构以及解离贴附动力学时, 理论计算与实验结果比较得出Becke3-LYP方法是合理的,然而在CH2ClCN-→CH2CN+Cl-的解离势能曲线的计算中,MP2和Becke3-LYP方法有显著的不同.
关键词:  卤代乙腈,电子贴附,解离动力学,电子相关效应
DOI:10.1088/1674-0068/21/03/255-262
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