Theoretical Studies on the Structures and Second-order Nonlinear Optical Properties of 12-Vertex Fluorocarborane Molecules†

doi:10.7503/cjcu20140605

Abstract

Abstract:

The structures and second-order nonlinear optical(NLO) properties of tetrafluoro carborane and its derivatives were investigated with density functional theory method. The results indicate that elongating the conjugation or enhancing the strength of donor(D) and acceptor(A) groups affect the distances of the carborane cage. Generally speaking, the dipole moment of molecule is determined by the D/A strengths, that is, the stronger D/A groups the larger dipole moment. Meanwhile, the polarizability of each molecule increases with the increasing of the conjugation and volume of substituents. Introducing the substituents with strong electron-withdrawing abilities or promoting the conjugation of substituents can effectively improve the second-order NLO coefficients. Furthermore, from the analysis of electronic absorption spectrum and the corresponding molecular orbit compositions, charge transfer pattern that comes from the carborane cage to the acene substituent illustrates the first hyperpolarizability value of molecule 4a' is the largest.

Key words: Fluorocarborane, Dipole moment, Nonlinear optical(NLO) property, Density functional theory

CLC Number:

O641.12

TrendMD:

FANG Xinyan, WANG Wenyong, WANG Jiao, LI Xiaoqian, SONG Hongjuan, QIU Yongqing. Theoretical Studies on the Structures and Second-order Nonlinear Optical Properties of 12-Vertex Fluorocarborane Molecules^†[J]. Chem. J. Chinese Universities, 2014, 35(11): 2377.

Figures/Tables 10

References 26

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Molecule	C1—C2	C1—B(mean)	C2—B(mean)	B9—B12	B9—B(mean)	B12—B(mean)
1a	0.1624	0.1694	0.1694	0.1806	0.1800	0.1800
1b	0.1614	0.1697	0.1697	0.1789	0.1781	0.1781
1c	0.1622	0.1698	0.1697	0.1779	0.1775	0.1775
2a	0.1637	0.1706	0.1706	0.1812	0.1795	0.1795
3a	0.1639	0.1703	0.1703	0.1810	0.1796	0.1796
3a^[20]	0.1670	0.1717	0.1710	0.1816	0.1795	0.1800
4a	0.1645	0.1710	0.1710	0.1815	0.1794	0.1794
4a'	0.1642	0.1713	0.1713	0.1818	0.1794	0.1793
4a″	0.1642	0.1715	0.1715	0.1821	0.1793	0.1793

Molecule	C1—C2	C1—B(mean)	C2—B(mean)	B9—B12	B9—B(mean)	B12—B(mean)
1a	0.1624	0.1694	0.1694	0.1806	0.1800	0.1800
1b	0.1614	0.1697	0.1697	0.1789	0.1781	0.1781
1c	0.1622	0.1698	0.1697	0.1779	0.1775	0.1775
2a	0.1637	0.1706	0.1706	0.1812	0.1795	0.1795
3a	0.1639	0.1703	0.1703	0.1810	0.1796	0.1796
3a^[20]	0.1670	0.1717	0.1710	0.1816	0.1795	0.1800
4a	0.1645	0.1710	0.1710	0.1815	0.1794	0.1794
4a'	0.1642	0.1713	0.1713	0.1818	0.1794	0.1793
4a″	0.1642	0.1715	0.1715	0.1821	0.1793	0.1793

Molecule	Three-center bond
1a	C1—B4—B5, C2—B7—B11, B3—B4—B5, B4—B5—B9, B6—B10—B11, B7—B8—B12, B8—B9—B12, B9—B10—B12
1b	C1—B3—B4, C1—B4—B5, C1—B5—B6, C2—B3—B7, C2—B6—B11, B3—B3—B8, B4—B5—B9, B5—B6—B10,
	B7—B8—B12, B7—B11—B12, B8—B9—B12, B9—B10—B12

Molecule	Three-center bond
1a	C1—B4—B5, C2—B7—B11, B3—B4—B5, B4—B5—B9, B6—B10—B11, B7—B8—B12, B8—B9—B12, B9—B10—B12
1b	C1—B3—B4, C1—B4—B5, C1—B5—B6, C2—B3—B7, C2—B6—B11, B3—B3—B8, B4—B5—B9, B5—B6—B10,
	B7—B8—B12, B7—B11—B12, B8—B9—B12, B9—B10—B12

Molecule	NBO charge/e			10³⁰ μ_z/(C·m)	10³⁰ μ/(C·m)	α_s/a.u.
Molecule	Ⅰ			10³⁰ μ_z/(C·m)	Ⅱ	Ⅲ
1a	-1.786	1.786		23.0	23.0	122.8
1b	-0.382	0.382		29.0	29.0	172.4
1c	-1.228	1.228		27.3	27.3	183.3
2a	-1.794	1.520	0.274	28.9	28.9	163.1
3a	-1.792	1.552	0.240	30.3	30.3	208.2
4a	-1.788	1.551	0.266	44.0	44.0	165.1
4a'	-1.788	1.525	0.264	30.4	30.4	223.7
4a″	-1.789	1.517	0.272	33.4	33.4	296.4