Theoretical Studies on Structures and Nonlinear Optical Properties of Superalkali-based Electrides Li3@calix[4]pyrrole and Li3O@calix[4]pyrrole†

doi:10.7503/cjcu20131229

Abstract

Abstract:

The geometrical structures, relative stabilities and nonlinear optical properties of superalkali-based electrides Li₃@calix[4]pyrrole and Li₃O@calix[4]pyrrole were studied in theory. Four and two isomers were identified for Li₃@calix[4]pyrrole and Li₃O@calix[4]pyrrole, respectively. The results show that, replacing alkali metal with superalkalis brings larger NLO responses to the electrides. In addition, the Li₃ and Li₃O molecules are ionized to a greater degree when they are parallel to the plane composed by four N atoms of the calix[4]pyrrole complexant. As a result, such structures exhibit larger first hyperpolarizabilities(β₀) than the other isomers.

Key words: Electride, Density functional theory, Superalkali, First hyperpolarizability, Nonlinear optical property

CLC Number:

O641

TrendMD:

HOU Na, LI Ying, WU Di, LI Zhiru. Theoretical Studies on Structures and Nonlinear Optical Properties of Superalkali-based Electrides Li₃@calix[4]pyrrole and Li₃O@calix[4]pyrrole^†[J]. Chem. J. Chinese Universities, 2014, 35(4): 798.

Figures/Tables 4

References 29

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System	Isomer	E_rel	Symmetry	d(Li1—Li2)	d(Li1—Li3)	ÐLi1—Li2—Li3	E_int
Li₃@calix[4]pyrrole	1	0	C_s	0.3019	0.2840	58.0	-146.52
	2	2.64	C_s	0.2813	0.2941	61.4	-145.23
	3	16.53	C₂_v	0.3225	0.2939	56.7	-124.98
	4	29.16	C₂_v	0.3257	0.2956	56.6	-106.61
System	Isomer	E_rel	Symmetry	d(Li1—O)	d(Li2—O)	ÐLi1(3) —O—Li2	E_int
Li₃O@calix[4]pyrrole	1'	0	C_s	0.1692	0.1690	118.3(111.6)	-145.18
	2'	34.39	C₂	0.1878	0.1768	137.6	-36.48

System	Isomer	E_rel	Symmetry	d(Li1—Li2)	d(Li1—Li3)	ÐLi1—Li2—Li3	E_int
Li₃@calix[4]pyrrole	1	0	C_s	0.3019	0.2840	58.0	-146.52
	2	2.64	C_s	0.2813	0.2941	61.4	-145.23
	3	16.53	C₂_v	0.3225	0.2939	56.7	-124.98
	4	29.16	C₂_v	0.3257	0.2956	56.6	-106.61
System	Isomer	E_rel	Symmetry	d(Li1—O)	d(Li2—O)	ÐLi1(3) —O—Li2	E_int
Li₃O@calix[4]pyrrole	1'	0	C_s	0.1692	0.1690	118.3(111.6)	-145.18
	2'	34.39	C₂	0.1878	0.1768	137.6	-36.48

System	Isomer	q(Li/Li₃/Li₃O)/e	VIE/eV	μ₀/a.u.	α₀/a.u.	β₀/a.u.
Li₃@calix[4]pyrrole	1	0.581	3.47	1.403	477.5	11444
	2	0.536	3.43	1.304	484.3	12479
	3	0.500	3.46	2.113	500.8	6047
	4	0.458	3.31	2.367	536.2	6476
Li₃O@calix[4]pyrrole	1'	0.648	3.39	1.926	424.5	16188
	2'	-0.039	4.79	0.398	427.2	1237
Li@calix[4]pyrrole		0.151	3.87	1.201	384.8	10776

System	Isomer	q(Li/Li₃/Li₃O)/e	VIE/eV	μ₀/a.u.	α₀/a.u.	β₀/a.u.
Li₃@calix[4]pyrrole	1	0.581	3.47	1.403	477.5	11444
	2	0.536	3.43	1.304	484.3	12479
	3	0.500	3.46	2.113	500.8	6047
	4	0.458	3.31	2.367	536.2	6476
Li₃O@calix[4]pyrrole	1'	0.648	3.39	1.926	424.5	16188
	2'	-0.039	4.79	0.398	427.2	1237
Li@calix[4]pyrrole		0.151	3.87	1.201	384.8	10776

Theoretical Studies on Structures and Nonlinear Optical Properties of Superalkali-based Electrides Li₃@calix[4]pyrrole and Li₃O@calix[4]pyrrole^†

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