B_xS_y、B_xSe_y(x=1、2,y=1—6)团簇结构的计算模拟研究
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摘要
超卤素团簇具有比卤族元素更高的电子亲和能(EA)、强氧化性及反应活性,被广泛应用于材料改性及新材料的合成等众多领域。BO_2团簇分子属于超卤素,本文基于BO_2团簇分子,根据密度泛函理论,采用B3LYP/6-311+g(3df)理论计算方法,研究了B_xS_y、B_xSe_y(x=1、2,y=1—6)团簇的几何结构、电荷分布、前线轨道分布、磁学特性及超卤素特性。研究结果表明,BS_2、B_2S_5、B_2Se_4、B_2Se_5的电子亲和能均大于卤素原子(Cl)的电子亲和能3.6 eV,这些团簇结构属于新型的超卤素团簇,为实验上超卤素的合成提供了理论依据。
Superhalogen clusters exhibit higher electron affinity(EA) than halogen element, and strong oxidation and reactive activity, which are widely used in material modification and synthesis of new materials. Previous research works have recognized BO_2 cluster as a superhalogen cluster. Based on the structure of BO_2 cluster, theoretical calculation method of B3 LYP/6-311+g(3 df) according to the density functional theory was employed to study the geometrical structure, charge distribution, frontier orbital distribution, magnetic properties and superhalogen properties of the newly designed cluster molecules, B_xS_y, B_xSe_y(x=1,2, y=1—6). It could be found from the results that the BS_2,B_2S_5,B_2Se_4,B_2Se_5 all showed the electron affinity higher than 3.6 eV(Cl), which illustrated that these cluster structures belonged to novel superhalogen clusters. These research findings are expected to provide theoretical basis for the synthesis of superhalogen cluster experimentally.
Superhalogen clusters exhibit higher electron affinity(EA) than halogen element, and strong oxidation and reactive activity, which are widely used in material modification and synthesis of new materials. Previous research works have recognized BO_2 cluster as a superhalogen cluster. Based on the structure of BO_2 cluster, theoretical calculation method of B3 LYP/6-311+g(3 df) according to the density functional theory was employed to study the geometrical structure, charge distribution, frontier orbital distribution, magnetic properties and superhalogen properties of the newly designed cluster molecules, B_xS_y, B_xSe_y(x=1,2, y=1—6). It could be found from the results that the BS_2,B_2S_5,B_2Se_4,B_2Se_5 all showed the electron affinity higher than 3.6 eV(Cl), which illustrated that these cluster structures belonged to novel superhalogen clusters. These research findings are expected to provide theoretical basis for the synthesis of superhalogen cluster experimentally.
引文
1 Gutsev G L,Boldyrev A I.Journal of Physical Chemistry,1990,94(6),2256.
2 Lv B L.First-principles study on the structure and properties of nickel-base alloys and nickel-aluminum intermetallics.Ph.D.Thesis,Dalian University of Technology,China,2012 (in Chinese).吕柏林.镍基合金及镍铝金属间化合物的结构与性能的第一性原理研究.博士学位论文,大连理工大学,2012.
3 Wudl F.Accounts of Chemical Research,1984,17(6),227.
4 Arnold F.Nature,1980,284(5757),610.
5 Bartlett N,Lucier G,Shen C,et al.Journal of Fluorine Chemistry,1995,71(2),163.
6 Leuchtner R E,Harms A C,Jr A W C.Journal of Chemical Physics,1989,91(4),2753.
7 Khanna S N,Jena P.Chemical Physics Letters,1994,219(5),479.
8 Bergeron D E,Castleman A W,Morisato T,et al.Science,2004,304(5667),84.
9 Bergeron D E,Roach P J,Jr C A,et al.Science,2005,307(5707),231.
10 Zhai H J,Wang L M,Li S D,et al.Journal of Physical Chemistry A,2007,111(6),1030.
11 Pradhan K,Jena P.Journal of Chemical Physics,2011,135(14),115.
12 Koirala P,Pradhan K,Kandalam A K,et al.Journal of Physical Chemistry A,2013,117(6),1310.
13 Kandalam A K,Kiran B,Jena P,et al.Physical Chemistry Chemical Physics,2015,17(40),26589.
14 Tang C,Zheng T,Zhang X.Journal of Cluster Science,2017,28(3),905.
15 Fang H,Wang S,Liu J,et al.Journal of Materials Chemistry A,2017,5(26).13373.
16 Pradhan K,Jena P.Journal of Chemical Physics,2011,135(14),115.
17 Gutsev G L,Weatherford C A,Johnson L E,et al.Journal of Computational Chemistry,2012,33(4),416.
18 Feng Y,Xu H G,Hou G L,et al.Journal of University of Science and Technology of China,2013,43(5),369 (in Chinese).冯源,许洪光,候高垒,等.中国科学技术大学学报,2013,43(5),369.
19 Ding L P,Kuang X Y,Shao P,et al.Royal Society of Chemistry,2013,3(35),15449.
20 Gutsev G L.Chemical Physics,1981,56(3),277.
2 Lv B L.First-principles study on the structure and properties of nickel-base alloys and nickel-aluminum intermetallics.Ph.D.Thesis,Dalian University of Technology,China,2012 (in Chinese).吕柏林.镍基合金及镍铝金属间化合物的结构与性能的第一性原理研究.博士学位论文,大连理工大学,2012.
3 Wudl F.Accounts of Chemical Research,1984,17(6),227.
4 Arnold F.Nature,1980,284(5757),610.
5 Bartlett N,Lucier G,Shen C,et al.Journal of Fluorine Chemistry,1995,71(2),163.
6 Leuchtner R E,Harms A C,Jr A W C.Journal of Chemical Physics,1989,91(4),2753.
7 Khanna S N,Jena P.Chemical Physics Letters,1994,219(5),479.
8 Bergeron D E,Castleman A W,Morisato T,et al.Science,2004,304(5667),84.
9 Bergeron D E,Roach P J,Jr C A,et al.Science,2005,307(5707),231.
10 Zhai H J,Wang L M,Li S D,et al.Journal of Physical Chemistry A,2007,111(6),1030.
11 Pradhan K,Jena P.Journal of Chemical Physics,2011,135(14),115.
12 Koirala P,Pradhan K,Kandalam A K,et al.Journal of Physical Chemistry A,2013,117(6),1310.
13 Kandalam A K,Kiran B,Jena P,et al.Physical Chemistry Chemical Physics,2015,17(40),26589.
14 Tang C,Zheng T,Zhang X.Journal of Cluster Science,2017,28(3),905.
15 Fang H,Wang S,Liu J,et al.Journal of Materials Chemistry A,2017,5(26).13373.
16 Pradhan K,Jena P.Journal of Chemical Physics,2011,135(14),115.
17 Gutsev G L,Weatherford C A,Johnson L E,et al.Journal of Computational Chemistry,2012,33(4),416.
18 Feng Y,Xu H G,Hou G L,et al.Journal of University of Science and Technology of China,2013,43(5),369 (in Chinese).冯源,许洪光,候高垒,等.中国科学技术大学学报,2013,43(5),369.
19 Ding L P,Kuang X Y,Shao P,et al.Royal Society of Chemistry,2013,3(35),15449.
20 Gutsev G L.Chemical Physics,1981,56(3),277.