Electronic and Spectroscopic Properties of La₂@C₁₁₂ Isomers

Abstract

Among the 3352 isolated pentagon rule(IPR) isomers and 129073 non-IPR isomers satisfying adjacent pentagon pairs(APPs)≤2 of fullerene C₁₁₂, the lowest-energy IPR and non-IPR isomers of C₁₁₂ and C₁₁₂ ^6- have been fully screened by the density functional tight-binding(DFTB) and density functional theory(DFT) methods for studying the electronic and spectroscopic properties of La₂@C₁₁₂. The structural features and infrared and absorption spectra of those isomers were analyzed in detail, and the characteristic fingerprint absorption peaks were assigned. To clarify the relative stabilities of La₂@C₁₁₂ isomers at high temperature, entropy contributions were determined at the B3LYP level. IPR isomer La₂@C₁₁₂(C ₂:860136) is not the lowest-energy isomer but is one of the most important isomers. This is the first work that considers non-IPR C₁₁₂ isomers when exploring the structure and properties of La₂@C₁₁₂.

Keywords

C₁₁₂ fullerene / La-endohedral metallofullerene(La-EMF) / Thermostability / IR spectrum / UV-Vis spectrum

References

[1] Kroto H. W., Heath J. R., Curl R. F., Smalley R. E. Nature, 1985, 318: 162.

[2] Krätschmer W., Lamb L. D., Fostiropoulos K., Huffman D. R. Na-ture, 1990, 347: 354.

[3] Kadish K. M., Ruoff R. Fullerenes: Chemistry, Physics, and Technology, 2000, New York: Wiley-VCH.

[4] Schön J. H., Kloc Ch., Siegrist T., Steigerwald M., Svensson C., Batlogg B. Nature, 2011, 413: 831.

[5] Peet J., Soci C., Coffin R. C., Nguyen T. Q., Mikhailovsky A., Moses D., Bazan G. C. Appl. Phys. Lett., 2006, 89: 252105.

[6] Amer M. S., Busbee J. J. Phys. Chem. C, 2011, 115: 10483.

[7] Vakhrushev A. V., Suyetin M. V. Nanotechnology, 2009, 20: 125602.

[8] Tian W. Q., Chen D. L., Cui Y. H., Feng J. K. J. Comput. Theor. Nanosci., 2009, 6: 239.

[9] Zhou X., Li W. Q., Shao B., Tian W. Q. J. Phys. Chem. C, 2013, 117: 23172.

[10] Lu X., Feng L., Akasaka T., Nagase S. Chem. Soc. Rev., 2013, 41: 7723.

[11] Zhang X., Li X. D., Ma L. X. Chem. Res. Chinese Universities, 2014, 30(6): 1044.

[12] Tamm N. B., Sidorov L. N., Kemnitz E., Troyanov S. Angew. Chem. Int. Ed., 2009, 48: 9102.

[13] Yang S. F., Wei T., Kemnitz E., Troyanov S. I. Angew. Chem. Int. Ed., 2012, 51: 8239.

[14] Yang H., Jin H. X., Che Y. L., Hong B., Liu Z. Y., Gharamaleki J. A., Olmstead M. M., Balch A. L. Chem. Eur. J.: Chemistry., 2012, 18: 2792.

[15] Mercado B. Q., Jiang A., Yang H., Wang Z. M., Jin H. X., Liu Z. Y., Olmstead M. M., Balch A. L. Angew. Chem. Int. Ed., 2009, 48: 9114.

[16] Ravinder P., Subramanian V. Comput. Thero. Chem., 2012, 998: 106.

[17] Shao N., Gao Y., Zeng X. C. J. Phys. Chem. C, 2007, 111: 17671.

[18] Xu L., Cai W. S., Shao X. G. Comput. Mat. Sci., 2008, 41: 522.

[19] Xu L., Cai W. S., Shao X. G. J. Phys. Chem. A, 2006, 110: 9247.

[20] Zhao X., Slanina Z. Comput. Thero. Chem., 2003, 636: 195.

[21] Zhao X., Goto H., Slanina Z. Chem. Phys., 2004, 306: 93.

[22] Calaminici P., Geudtner G., Köster A. M. J. Chem. Theory. Comput., 2009, 5: 29.

[23] Popov A. A., Dunsch L. J. Am. Chem. Soc., 2007, 129: 11835.

[24] Yang T., Zhao X., Nagase S. Phys. Chem. Chem. Phys., 2001, 13: 5034.

[25] Guo Y. J., Yang T., Nagase S., Zhao X. Inorg. Chem., 2014, 53: 2012.

[26] Zhao X., Gao W. Y., Yang T., Zheng J. J., Li L. S., He L., Cao R. J., Nagase S. Inorg. Chem., 2012, 51: 2039.

[27] Lu X., Akasaka T., Nagase S. Rare Earth Coordination Chemistry: Fundamentals and Applications, 2009, Singapore: Wiley-Blackwell, 273.

[28] Brinkmann G., Friedrichs O. D., Lisken S., Peeters A., van Cleemput N. Match-Commun. Math. Comput. Chem., 2010, 63: 533.

[29] Porezag D., Frauenheim Th., Köhler Th., Seifert G., Kaschner R. Phys. Rev. B: Condens. Matter., 1995, 51: 12947.

[30] Bai H. C., Xue P., Tao J. Y., Ji W. X., Han Z. M., Ma Y. J., Ji Y. Q. Comput. Thero, Chem., 2015, 1069: 138.

[31] Casida M. E., Jamorski C., Casida K. C., Salahub D. R. J. Chem. Phys., 1998, 108: 4439.

[32] Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Peters-son G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmay-lov 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., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staro-verov 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 03, Revision E.01, 2003, Pittsburgh PA: Gaussian Inc..