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

doi:10.7503/cjcu20140513

Abstract

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

CLC Number:

O641

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2014, 35(11): 2390.

Figures/Tables 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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