Theoretical Studies on the Structure Stability and Magnetic Properties of SnnSm(n=1—9) Clusters†

doi:10.7503/cjcu20160318

Abstract

Abstract:

The geometrical structures, relative stabilities, electronic properties and magnetism of tin clusters and bimetallic complexes of tin clusters with one samarium atom Sn_nSm(n=1—9) were investigated with the Saunders “Kick” global stochastic search technique combined with density functional theory(DFT) calculations at the B3LYP/SDD level of theory. The results are as follows: (1) Samarium atom usually located on the surface in the doped tin-based with one samarium atom clusters. And the ground-state structures of the Sn_nSm(n=1—9) clusters prefer to three-dimensional structure with higher symmetry; (2) after doping samarium atom in the Sn-based cluster, the cluster has the increase average binding energy which should owe to the fact that the bonding energy of Sn—Sm bond is higher than Sn—Sn bond and has the stronger interaction; (3) the doped Sn-based with one samarium atom cluster has large magnetic moments, and the contribution of magnetic moment almost comes from 4f electron orbit of the samarium atom, while the contribution of tin atoms is negligible. With the increase of cluster’s size, bimetallic complexes cluster has the special phenomenon that the total magnetic moment tends to be stable.

Key words: Atomic cluster, Density functional theory, Magnetic moment, Kick model

CLC Number:

O641

TrendMD:

SUN Lin, WANG Huaiqian, WU Meng, LI Huifang, LI Xiaoyi, DU Dan, SHA Rui. Theoretical Studies on the Structure Stability and Magnetic Properties of Sn_nSm(n=1—9) Clusters^†[J]. Chem. J. Chinese Universities, 2016, 37(10): 1840.

Figures/Tables 9

Fig.1 Structure, symmetry point group and electronic state of the Snn(n=2—10) cluster, using B3LYP/SDD calculations

Table 1 Average binding energies of the Snn(n=2—10)

Structure	E_b/eV			Structure	E_b/eV
Structure	B3LYP/SDD		CCSD(T)/cc-pVTZ-PP	Expt.^[30]	B3LYP/SDD	CCSD(T)/cc-pVTZ-PP	Expt.^[30]
Sn₂	0.88	1.07	0.94	Sn₇	2.09	2.48	2.37
Sn₃	1.41	1.50	1.65	Sn₈	2.04
Sn₄	1.80	1.98	1.94	Sn₉	2.08
Sn₅	1.88	2.15	2.11	Sn₁₀	2.15
Sn₆	1.99	2.34	2.28

Fig.2 Structure, symmetry point group, electronic state and relative energy(eV) of the lower-lying isomers SnnSm(n=1—9) cluster

Fig.3 Average binding energy for the ground-state structures of SnnSm(a) and Snn+1(b) clusters and ΔEb(c)

Fig.4 Second order difference energy of SnnSm(a) and Snn+1(b) clusters

Fig.5 HOMO-LUMO energy gap of the ground-state structures of SnnSm clusters

Fig.6 Total magnetic moments of SnnSm clusters

Fig.7 Magnetic moments contribution of 6s,4f and 5d states for Sm atom in SnnSm clusters and local magnetic moments of the Sn and Sm atom

Table 2 Valence electron configuration of Sm atom in the SnnSm(n=1—9) cluster

Structure	Valence electron configuration
SnSm	6s^1.204f^6.005d^0.186p^0.06
Sn₂Sm	5p^0.036s^0.714f^5.985d^0.466p^0.03
Sn₃Sm	6s^0.664f^5.995d^0.406p^0.06
Sn₄Sm	6s^0.434f^5.995d^0.586p^0.09
Sn₅Sm	6s^0.494f^5.995d^0.576p^0.087p^0.02
Sn₆Sm	6s^0.354f^5.995d^0.806p^0.146d^0.017p^0.03
Sn₇Sm	4f^5.995d^0.716p^0.037s^0.287p^0.08
Sn₈Sm	6s^0.384f^5.995d^0.776p^0.166d^0.017p^0.13
Sn₉Sm	4f^5.985d^0.766p^0.056d^0.017p^0.048s^0.29

References 31

[1]	Jing Q., Ge G. X., Cao H. B., Huang X. C., Liu X. Y., Yang H. X., Acta Phys. -Chim. Sinia, 2010, 26(9), 2510—2514
	(井群, 葛桂贤, 曹海宾, 黄旭初, 刘效勇, 闫红霞.物理化学学报, 2010,26(9), 2510—2514)
[2]	Chen L., Xu C., Zhang X. F., Acta Phys. Sinica, 2009, 58(3), 1603—1607
	(陈亮, 徐灿, 张小芳.物理学报, 2009,58(3), 1603—1607)
[3]	Lu Z. H., Cao J. X., Chin. Phys. B, 2008, 17(9), 3336—3342
[4]	Zhang C. R., Chen Y. H., Wang D. B., Wu Y. Z., Chen H. S., Chin. Phys. B, 2008, 17(8), 2938—2950
[5]	Baletto F., Ferrando R., Rev. Mod. Phys., 2005, 77(1), 371—423
[6]	Jones R. O., J. Chem. Phys., 1999, 110(11), 5189—5200
[7]	Handschuh H., Gantefor G., Kessler B., Bechthold P. S., Eberhardt W., Phys. Rev. Lett., 1995, 74(7), 1095—1098
[8]	Yoo S., Zeng X. C., J. Chem. Phys., 2006, 124(5), 054304
[9]	Qin W., Lu W. C., Zhao L. Z., Zang Q. J., Chen G. J., Wang C. Z., Ho K. M., J. Chem. Phys., 2009, 131(12), 124507
[10]	Li X. P., Lu W. C., Zang Q. J., Chen G. J., Wang C. Z., Ho K. M., J. Phys. Chem. A, 2009, 113,6217—6221
[11]	Zhu X. L., Zeng X. C., Lei Y. A., Pan B. C., J. Chem. Phys., 2004, 120(19), 8985—8995
[12]	Zhao L. Z., Lu W. C., Qin W., Zang Q. J., Wang C. Z., Ho K. M., J. Phys. Chem. A, 2008, 112(26), 5815—5823
[13]	Drebov N., Oger E., Rapps T., Kelting R., Schooss D., Weis P., Kappes M. M., Ahlrichs R., J. Chem. Phys., 2010, 133(22), 224302
[14]	Zang Q. J., Chen G. J., Qin W., Zhao L. Z., Lu W. C., Chem. Res. Chinese Universities, 2013, 29(3), 579—583
[15]	Clayborne P. A., Gupta U., Reber A. C., Melko J. J., Khanna S. N., Castleman A. W. Jr, J. Chem. Phys., 2010, 133(13), 134302
[16]	Barman S., Rajesh C., Das G. P., Majumder C., Eur. Phys. J. D, 2009, 55,613—625
[17]	James H., Arif I., Giorgi J. B., Tom K. W., Phys. Chem. Chem. Phys., 2010, 12,12969—12972
[18]	Fang X. W., Wang C. Z., Yao Y. X., Ding Z. J., Hupalo M., Tringides M. C., Ho K. M., Phys. Rev. B, 2011, 83(22), 224203
[19]	Negrier M., Tuaillon-Combes J., Dupuits V., Perez A., Pellarin M., Broyer M., Eur. Phys. J. D, 1999, 9,475—478
[20]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A. Jr., Peralta J. E., Ogliaor F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Keith T., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision C.01, Gaussian Inc., Wallingford CT, 2010
[21]	Wang H. Q., Li H. F., Zheng L. X., J. Magn. Magn. Mater., 2013, 344,79—84
[22]	Li H. F., Wang H. Q., Phys. Chem. Chem. Phys., 2014, 16,244—254
[23]	Wang H. Q., Li H. F., Kuang X. Y., Phys. Chem. Chem. Phys., 2012, 14,5272—5283
[24]	Wang H. Q., Li H. F., J. Chem. Phys., 2012, 137(16), 164304
[25]	Wang H. Q., Li H. F., Wang J. X., Kuang X. Y., J. Mol. Model., 2012, 18,2993—3001
[26]	Bera P. P., Sattelmeyer K. W., Saunders M., Schaefer III H. F., Schleyer P. R., J. Phys. Chem. A, 2006, 110(13), 4287—4290
[27]	Becke A. D., J. Chem. Phys., 1993, 98(7), 5648—5652
[28]	Bartlett R. J., Musial M., Rev. Mod. Phys., 2007, 79(1), 291—352
[29]	Peterson K. A., J. Chem. Phys., 2003, 119(21), 11099—11112
[30]	Gingerich K. A., Desideri A., Cocke D. L., J. Chem. Phys., 1975, 62(2), 731—732
[31]	Assadollahzadeh B., Schafer S., Schwerdtfeger P., J. Comput. Chem., 2010, 31(5), 929—937