Nonlinear optical response of endohedral all-metal electride cages 2e−Mg2+(M@E12)2−Ca2+ (M = Ni, Pd, and Pt; E = Ge, Sn, and Pb). Issue 3 (2nd January 2019)

• Record Type: Journal Article
• Authors: He, Hui-Min; Luis, Josep M.; Chen, Wei-Hong; Yu, Dan; Li, Ying; Wu, Di; Sun, Wei-Ming; Li, Zhi-Ru
• Is Part Of: Journal of materials chemistry. Volume 7:Issue 3(2019)
• Page Start: 645
• Page End: 653
• Publication Date: 2019-01-02
• Subjects: Materials -- Periodicals; Chemistry, Analytic -- Periodicals; Optical materials -- Research -- Periodicals; Electronics -- Materials -- Research -- Periodicals; 543.0284
• DOI: 10.1039/c8tc05647a
• Languages: English
• ISSNs: 2050-7526

Abstract

Abstract : The endohedral all-metal electride cages 2e − Mg 2+ (M@E12 ) 2− Ca 2+ (M = Ni, Pd, and Pt; E = Ge, Sn, and Pb) exhibit a better NLO response. Abstract : To extend the interesting new concept of the all-metal electride, a series of endohedral all-metal electride cages 2e − Mg 2+ (M@E12 ) 2− Ca 2+ (E = Ge, Sn, and Pb; M = Ni, Pd, and Pt) has been designed and investigated theoretically using the exchange–correlation functional CAM-B3LYP. In these electride cage molecules with excess electrons, interesting pull–push electron transfer relay occurs. The metal cage M@E12 first pulls valence electrons from Ca atom forming a polyanion (M@E12 ) 2−, and then the formed polyanion pushes valence electrons of Mg atom out of its valence shell generating the isolated excess electrons that characterize this species as all-metal electrides. These endohedral all-metal electride cages display a large electronic first hyperpolarizability ( β e0) and so they could have a potential application as a new kind of second-order nonlinear optical (NLO) material. We have explored the structure–property relationships, which are significant. It is shown that, for a given central atom, the all-metal electrides with a Sn-cage correspond to the largest β e0, whereas, for a given metal cage, the all-metal electrides with Ni as the central atom correspond to the largest β e0. Owing to the two effects, the endohedral all-metal electride cage 2e − Mg 2+ (Ni@Sn12 ) 2− Ca 2+ exhibits the largest β e0 value (16 893 a.u.). The same conclusions are also valid for the frequency-dependent β e (−2 ω ; ω, ω ) and β e (− ω ; ω, 0). Moreover, we have also explored the role of the vibrational contribution in the largest components (in x -axis) of static β for endohedral all-metal electride cages. The vibrational contributions are significant for new all-metal electride NLO properties and therefore should be considered in the design of new NLO all-metal electrides.