表面吸附碱金属原子的超短碳纳米管体系的结构和非线性光学性质

doi:10.7503/cjcu20140513

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (11): 2390.doi: 10.7503/cjcu20140513

表面吸附碱金属原子的超短碳纳米管体系的结构和非线性光学性质

李绍晨, 于广涛, 陈巍(), 黄旭日()

吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023

收稿日期:2014-06-06 出版日期:2014-11-10 发布日期:2014-09-28
作者简介:联系人简介: 黄旭日, 男, 博士, 教授, 博士生导师, 主要从事功能材料设计研究和化学微观反应机理研究. E-mail:huangxr@jlu.edu.cn;陈巍, 女, 博士, 教授, 博士生导师, 主要从事低维纳米材料和革新非线性光学材料的结构与性能研究. E-mail:w_chen@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 21103065, 21373099, 21173097)、国家“九七三”计划项目(批准号: 2012CB932800)和教育部博士点基金(批准号: 20110061120024, 20130061110020) 资助

Investigation on Structures and Nonlinear Optical Properties of Super-short Carbon Nanotube Systems with Surface-adsorbing Lithium Atoms^†

LI Shaochen, YU Guangtao, CHEN Wei^*(), HUANG Xuri^*()

State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China

Received:2014-06-06 Online:2014-11-10 Published:2014-09-28
Contact: CHEN Wei,HUANG Xuri E-mail:w_chen@jlu.edu.cn;huangxr@jlu.edu.cn
Supported by:
† Supported by the National Natural Science of China(Nos. 21103065, 21373099, 21173097), the National Basic Research Program of China(No. 2012CB932800) and the Specialized Research Fund for the Doctoral Program of Higher Education of China(Nos. 20110061120024, 20130061110020).

摘要/Abstract

摘要：

采用密度泛函理论(DFT)方法系统研究了表面吸附碱金属Li原子的超短碳纳米管([8]cyclophe-nacene)体系的结构和非线性光学性质. 在这些体系中, Li原子均能稳定地吸附在超短碳纳米管表面, 其吸附能高达84.0~106.2 kJ/mol. 当吸附1~2个Li原子时, Li原子和碳纳米管之间发生了明显的电荷转移过程, 使体系的一阶超极化率(β₀)值明显改善, β₀值从0迅速增加到3.42×10³~8.29×10³ a.u.; 当吸附的Li原子数增加到3时, 体系内部产生了额外电子, 有效地降低了体系最主要跃迁的跃迁能, 使体系的一阶超极化率进一步提升(高达2.59×10⁶a.u.). 此外, Li原子之间的距离也是影响吸附体系β₀值的重要因素.

关键词: 碱金属原子, 超短碳纳米管, 一阶超极化率, 电荷转移, 额外电子, 表面吸附, 非线性光学性质

Abstract:

Under the density functional theory(DFT) method, the structures and nonlinear optical(NLO) properties of seven new Li_n@cyclophenacene(n=1—3) species were investigated in detail, where one to three Li atoms are adsorbed over the surface of the super-short carbon nanotube([8]cyclophenacene). In these systems, the Li atoms can be adsorbed stably on the nanotube, as revealed by their considerable adsorption energies(84.0—106.2 kJ/mol). Besides, when adsorbing one to two alkali Li atoms, the first hyperpolarizability of the carbon nanotube can be effectively improved, where the β₀ value can be significantly increased from zero to the range of 3.42×10³—8.29×10³ a.u., owing to the occurrence of charge transfer process from the Li atom to the nanotube. Comparatively, when increasing the number of the adsorbed Li atoms to three, the β₀ value can be further enhanced sharply, even to as large as 2.59×10⁶ a.u., which can be attributed to the formation of the excess electron. Moreover, the distance between the adsorbed Li atoms can also play an important role in effecting the first hyperpolarizabilities of systems. This work can provide some new valuable insights for designing the new type of high-performance NLO materials based on the carbon nanotubes.

Key words: Alkali metal atom, Super-short carbon nanotube, First hyperpolarizability, Charge transfer, Excess electron, Surface-adsorption, Nonlinear optical property

中图分类号:

O641

TrendMD:

李绍晨, 于广涛, 陈巍, 黄旭日. 表面吸附碱金属原子的超短碳纳米管体系的结构和非线性光学性质. 高等学校化学学报, 2014, 35(11): 2390.

LI Shaochen, YU Guangtao, CHEN Wei, HUANG Xuri. Investigation on Structures and Nonlinear Optical Properties of Super-short Carbon Nanotube Systems with Surface-adsorbing Lithium Atoms^†. Chem. J. Chinese Universities, 2014, 35(11): 2390.

图/表 4

Fig.1 Optimized geometries of Li1@cyclophenace [the side(A) and top(A') views] and Lin@cyclophenace [n=2(B1—B3) and n=3(C1—C3)] (A) The “d” represents the vertical distance between the doped Li atom and super-short carbon nanotube. (B1) Li2a@cyclophenace; (B2) Li2b@cyclophenace; (B3) Li2c@cyclophenace; (C1) Li3a@cyclophenace; (C2) Li3b@cyclophenace; (C3) Li3c@cyclophenace.

Table 1 Adsorption energies(Ead) of doped Li atoms in the Lin@cyclophenace series(n=1—3) and their corresponding vertical distances(d) between the Li atom and carbon nanotube

System	d/nm	E_ad/(kJ·mol^-1)	System	d/nm	E_ad/(kJ·mol^-1)
Li₁@cyclophenace	0.171	84.0	Li_3a@cyclophenace	0.228^*	99.1
Li_2a@cyclophenace	0.205	106.2	Li_3b@cyclophenace	0.228^*	99.5
Li_2b@cyclophenace	0.204	106.2	Li_3c@cyclophenace	0.223^*	85.7
Li_2c@cyclophenace	0.205	104.9

Table 2 Polarizability(α), the first hyperpolarizability(β0), the oscillator strengh(f0), the transition energy(ΔE), the difference of dipole moments(Δμ) between the crucial excited state and ground state, the estimated β0 values under the two-level approach, and the main compositions of the crucial transition(CT) state for the Lin@cyclophenace(n=1—3) series*

System	α/a.u.	β₀/a.u.	f₀/a.u.	ΔE/eV	Δμ/a.u.	(Δμ·f₀)/ΔE³	CT
Cyclophenace	312	0	0.1483	4.260	0	0
Li₁@cyclophenace	374	8.29×10³	0.0368	1.778	3.174	418	H→L+3 H→L+4
Li_2a@cyclophenace	378	6.94×10³	0.1190	2.236	1.747	374	H→L+4 H→L+8
Li_2b@cyclophenace	409	4.46×10³	0.0973	2.166	1.437	277	H→L+4 H→L+5
Li_2c@cyclophenace	421	3.42×10³	0.0908	2.055	0.684	144	H→L+4 H-1→L
Li_3a@cyclophenace	529	8.44×10³	0.0933	1.446	0.800	497	H→L+5 H→L+6
Li_3b@cyclophenace	520	1.11×10⁴	0.0914	1.431	1.194	749	H→L+4 H→L+5
Li_3c@cyclophenace	2814	2.59×10⁶	0.0868	1.247	2.411	2172	H→L+9 H→L+10

Fig.2 Crucial transition states of the Lin@cyclophenace(n =1—3) systems (A) Li1@cyclophenace; (B)Li2a@cyclophenace; (C) Li2b@cyclophenace; (D) Li2c@cyclophenace; (E) Li3a@cyclophenace; (F) Li3b@cyclophenace; (G) Li3c@cyclophenace. The relatively large component coefficients are marked.

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表面吸附碱金属原子的超短碳纳米管体系的结构和非线性光学性质

Investigation on Structures and Nonlinear Optical Properties of Super-short Carbon Nanotube Systems with Surface-adsorbing Lithium Atoms^†

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表面吸附碱金属原子的超短碳纳米管体系的结构和非线性光学性质

Investigation on Structures and Nonlinear Optical Properties of Super-short Carbon Nanotube Systems with Surface-adsorbing Lithium Atoms†

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Investigation on Structures and Nonlinear Optical Properties of Super-short Carbon Nanotube Systems with Surface-adsorbing Lithium Atoms^†