caa a22 4500 605512132 CHVBK 20210128100654.0 cr unu---uuuuu 210128e20151001xx s 000 0 eng 10.1007/s00894-015-2808-9 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2808-9 Charge transfer and first hyperpolarizability: cage-like radicals C59X and lithium encapsulated LiC59X (X=B, N) [Elektronische Daten] [Feng-Wei Gao, Rong-Lin Zhong, Shi-Ling Sun, Hong-Liang Xu, Liang Zhao, Zhong-Min Su] Very recently, two new cage-like radicals (C59B and C59N) formed by a boron or nitrogen atom substituting one carbon atom of C60 were synthesized and characterized. In order to explore the structure-property relationships of combination the cage-like radical and alkali metal, the endohedral Li@C59B and Li@C59N are designed by lithium (Li) atom encapsulated into the cage-like radicals C59B and C59N. Further, the structures, natural bond orbital (NBO) charges, and nonlinear optical (NLO) responses of C59B, C59N, Li@C59B, and Li@C59N were investigated by quantum chemical method. Three density functional methods (BHandHLYP, CAM-B3LYP, and M05-2X) were employed to estimate their first hyperpolarizabilities (β tot) and obtained the same trend in the β tot value. The β tot values by BHandHLYP functional of the pure cage-like radicals C59B (1.30 × 103 au) and C59N (1.70 × 103 au) are close to each other. Interestingly, when one Li atom encapsulated into the electron-rich radical C59N, the β tot value of the Li@C59N increases to 2.46 × 103 au. However, when one Li atom encapsulated into the electron-deficient radical C59B, the β tot value of the Li@C59B sharply decreases to 1.54 × 102 au. The natural bond orbital analysis indicates that the encapsulated Li atom leads to an obvious charge transfer and valence electrons distribution plays a significant role in the β tot value. Further, frontier molecular orbital explains that the interesting charge transfer between the encapsulated Li atom and cage-like radicals (C59B and C59N) leads to differences in the β tot value. It is our expectation that this work will provide useful information for the design of high-performance NLO materials. Springer-Verlag Berlin Heidelberg, 2015 Alkali metal nationallicence Cage-like radical nationallicence Charge transfer nationallicence First hyperpolarizability nationallicence NLO nationallicence Gao Feng-Wei Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut Zhong Rong-Lin Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut Sun Shi-Ling Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut Xu Hong-Liang Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut Zhao Liang Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut Su Zhong-Min Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/10(2015-10-01), 1-6 1610-2940 21:10<1 2015 21 894 https://doi.org/10.1007/s00894-015-2808-9 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2808-9 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Gao Feng-Wei Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut NATIONALLICENCE 700 1- Zhong Rong-Lin Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut NATIONALLICENCE 700 1- Sun Shi-Ling Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut NATIONALLICENCE 700 1- Xu Hong-Liang Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut NATIONALLICENCE 700 1- Zhao Liang Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut NATIONALLICENCE 700 1- Su Zhong-Min Institute of Functional Material Chemistry, Department of Chemistry, Northeast Normal University, 130024, Changchun, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/10(2015-10-01), 1-6 1610-2940 21:10<1 2015 21 894