(BN)_(25)团簇的结构与性能
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摘要
采用密度泛函理论的杂化密度泛函(B3LYP)方法,在6-31G(d)基组水平上,对(BN)_(25)团簇进行结构优化和频率计算,得到基态构型,并对其稳定性、自然键轨道(NBO)、振动光谱和NICS进行计算.结果表明:(BN)_(25)团簇的能隙值较高,具有良好的化学稳定性;B原子和N原子的内部及原子之间都会发生s、p轨道杂化,原子之间有少量电荷转移;(BN)_(25)团簇的红外光谱和拉曼光谱都有较多振动峰;(BN)_(25)团簇具有芳香性.
Geometries, stabilities, NBO, vibrational spectroscopy and NICS of(BN)_(25) clusters were optimized in the framework of density functional theory(DFT) through the use of B3LYP hybrid functional associated with 6-31 G(d) basis sets. We found that(BN)_(25) clusters is stable due to its large average binding energy and energy gap. Charge transfer and s, p hybridization between adjacent B and N atoms are confirmed by NBO analysis. Many vibration peaks are found in infrared spectrum and Raman spectra. Negative nucleus independent chemical shifts(NICS) indicate that BN clusters have aromatic properties.
Geometries, stabilities, NBO, vibrational spectroscopy and NICS of(BN)_(25) clusters were optimized in the framework of density functional theory(DFT) through the use of B3LYP hybrid functional associated with 6-31 G(d) basis sets. We found that(BN)_(25) clusters is stable due to its large average binding energy and energy gap. Charge transfer and s, p hybridization between adjacent B and N atoms are confirmed by NBO analysis. Many vibration peaks are found in infrared spectrum and Raman spectra. Negative nucleus independent chemical shifts(NICS) indicate that BN clusters have aromatic properties.
引文
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[3] HUO P Y, ZHANG X R, YU Z C, et al. DFT study of NO and H2O co-adsorption on CumCon(m+n=2～7) clusters[J]. J Mol Struct,2017,1148(15):486-495.
[4] ZHANG X R, LUO M, GUO W L. Theoretical study on structure stability and magnetic properties of (OsH2)n(n=1-5)clusters[J]. Chinese Journal of Computational Physics,2015,32(2):220-228.
[5] GUO J, SHENG Z Q, MENG Y, et al. Growth dynamics and energy of C36 cluster[J]. Chinese Journal of Computational Physics,2014,31(2):247-252.
[6] IIJIMA S. Helical microtubules of graphitic carbon[J]. Nature,1991,354(7):56-58.
[7] 贾建峰, 武海顺, 焦海军. (BN)n团簇的结构和稳定性[J]. 化学学报,2003, 61(5): 653-659.
[8] SUN M L, SLANINA Z, LEE S L. Square/hexagon route towards the boron-nitrogen clusters[J]. Chem Phys Lett,1995,233(3):279-283.
[9] SEIFERT G, FOWLER P W, MITECHELL D, et al. Boron-nitrogen analogues of the fullerenes: Electronic and structural properties[J]. Chem Phys Lett,1997,268(5/6):352-358.
[10] STROUT D L J. Structure and stability of boron nitrides:Isomers of B12N12[J]. Journal of Physical Chemistry A,2000,104(15):3364-3366.
[11] 宋燕, 陈宏善, 张材荣, 等. (BN)n(n≤12)团簇的结构及成键性质[J]. 物理化学学报,2005,21(7):735-739.
[12] ROGERS K M, FOWLER P W, SEIFERT G. Chemical versus steric frustration in boron nitride heterofullerene polyhedra[J]. Chem Phys Lett,2000,332(1/2):43-50.
[13] ALEXANDRE S S, MAZZONI M S C, CHACHAM H. Stability, geometry,and electronic structure of the boron nitride B36N36 fullerene[J]. Applied Physics Letters,1999,75(1):61-64.
[14] WU H S, XU X H, ZHANG F Q, et al. New boron nitride B24N24 nanotube [J]. J Phys Chem A,2003,107(34):6609-6612.
[15] ZHANG X R, YIN L, LI W J, et al. Density functional theory study of structure and stability of WmBn(m+n≤7) clusters[J].Chinese Journal of Computational Physics,2013,30(5):775-782.
[16] 张秀荣, 李扬, 杨星. WnNim(n+m=8)团簇结构与电子性质的理论研究[J]. 物理学报,2011,60(10):236-245.
[17] ZHANG X R, LI Y, YIN L. Theoretical study of molecular oribital energy levels and aromaticity of WnNim(n+m=8) clusters[J]. Chinese Journal of Computational Physics,2012,29(6):912-920.