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)

He, Huimin; Luis, Josep M.; Chen, Weihong; Yu, Dan; Li, Ying; Wu, Di; Sun, Wei‐Ming; Li, Zhi‐Ru

doi:10.1039/c8tc05647a

Cited by 17 publications

(11 citation statements)

References 61 publications

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“…The excited states were calculated using the TD-CAM-B3LYP method. 49,[66][67][68][69][70] Topological analysis of electron density was performed using the MP2 method since Timerghazin and Peslherbe have shown that the characterization of excess electrons is sensitive to electron correlation and large basis sets. 71 The topological analysis of atoms in molecules (AIM) 72,73 and the electron localization function (ELF) [74][75][76] were conducted by using the free and open source Multiwfn program.…”

Section: Methodsmentioning

confidence: 99%

Theoretical study of substituent effects on electride characteristics and the nonlinear optical properties of Li@calix[4]pyrrole

et al. 2019

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Section: Methodsmentioning

confidence: 99%

Theoretical study of substituent effects on electride characteristics and the nonlinear optical properties of Li@calix[4]pyrrole

et al. 2019

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“…The VIE is the energy difference between neutral molecule and cation systems at the neutral optimization geometry (Wang et al, 2012;Bai et al, 2013;Sun et al, 2015;He et al, 2019).…”

Section: Computational Detailsmentioning

confidence: 99%

“…Therefore, selecting the proper excess electron source to achieve new excess electron compounds will be an efficient way to obtain NLO materials with high stability. To achieve this aim, we have used alkaline-earth metal atoms as an electron source to design several types of excess electron compounds (He et al, 2017a;He et al, 2017b;He et al, 2019) with large first hyperpolarizabilities and satisfying stability.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Alkaline-Earth Metal (Be, Mg, and Ca)-Substituted Aluminum Nitride Nanocages With High Stability and Large Nonlinear Optical Responses

He¹,

Yang²,

et al. 2022

Front. Chem.

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By replacing one Al or N atom of aluminum nitride nanocage Al12N12 with an alkaline-earth metal atom, two series of compounds, namely, M@Al12N11 and M@Al11N12 (M = Be, Mg, and Ca), were constructed and investigated in theory. The substituted effect of alkaline-earth metal on the geometric structure and electronic properties of Al12N12 is studied in detail by density functional theory (DFT) methods. The calculated binding energies, HOMO–LUMO gaps, and VIE values of these compounds reveal that they possess high stability, though the NBO and HOMO analyses show that they are also excess electron compounds. Due to the existence of diffuse excess electrons, these alkaline-earth metal-substituted compounds exhibit larger first hyperpolarizabilities (β0) than pure Al12N12 nanocage. In particular, these considered compounds exhibit satisfactory infrared (IR) (>1800 nm) and ultraviolet (UV) (˂ 250 nm) transparency. Therefore, these proposed excess electron compounds with high stability may be regarded as potential candidates for new UV and IR NLO molecules.

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“…There are, however, other electrides that have been suggested in the literature based on computational calculations. 43,44 This is the case of molecular electrides, 45 which are single-molecule electrides, or metal cluster electrides, 46 in which a sea of delocalized valence electrons surround the metal cation.…”

Section: ■ Introductionmentioning

confidence: 99%

How Many Electrons Does a Molecular Electride Hold?

et al. 2021

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Electrides are very peculiar ionic compounds where electrons occupy the anionic positions. In a crystal lattice, these isolated electrons often form channels or surfaces, furnishing electrides with many traits with promising technological applications. Despite their huge potential, thus far, only a few stable electrides have been produced because of the intricate synthesis they entail. Due to the difficulty in assessing the presence of isolated electrons, the characterization of electrides also poses some serious challenges. In fact, their properties are expected to depend on the arrangement of these electrons in the molecule. Among the criteria that we can use to characterize electrides, the presence of a non-nuclear attractor (NNA) of the electron density is both the rarest and the most salient feature. Therefore, a correct description of the NNA is crucial to determine the properties of electrides. In this paper, we analyze the NNA and the surrounding region of nine molecular electrides to determine the number of isolated electrons held in the electride. We have seen that the correct description of a molecular electride hinges on the electronic structure method employed for the analyses. In particular, one should employ a basis set with sufficient flexibility to describe the region close to the NNA and a density functional approximation that does not suffer from large delocalization errors. Finally, we have classified these nine molecular electrides according to the most likely number of electrons that we can find in the NNA. We believe this classification highlights the strength of the electride character and will prove useful in designing new electrides.

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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)

Abstract: The endohedral all-metal electride cages 2e−Mg2+(M@E12)2−Ca2+ (M = Ni, Pd, and Pt; E = Ge, Sn, and Pb) exhibit a better NLO response.

Cited by 17 publications

References 61 publications

Theoretical study of substituent effects on electride characteristics and the nonlinear optical properties of Li@calix[4]pyrrole

Theoretical study of substituent effects on electride characteristics and the nonlinear optical properties of Li@calix[4]pyrrole

Theoretical Study of Alkaline-Earth Metal (Be, Mg, and Ca)-Substituted Aluminum Nitride Nanocages With High Stability and Large Nonlinear Optical Responses

How Many Electrons Does a Molecular Electride Hold?

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