In:
Dalton Transactions, Royal Society of Chemistry (RSC), Vol. 51, No. 21 ( 2022), p. 8437-8453
Abstract:
Mixed superalkali clusters are a source of excess electrons, as their vertical ionization energies (2.81–3.36 eV) are much lower than those of alkali metals (even cesium (∼3.85 eV)) and the superalkali Li 3 O (3.42 eV). In the present work, the geometric, electronic, and nonlinear optical (NLO) properties of mixed superalkali cluster-doped B 12 N 12 nanocages are studied theoretically. All complexes, A–G, have very high interaction energies (−98.02 to −123.13 kcal mol −1 ) and are thermodynamically stable when compared to previously reported Li 3 O@B 12 N 12 (−92.71 kcal mol −1 ). The designed complexes have smaller HOMO–LUMO energy gaps (3.36–4.27 eV) than pristine B 12 N 12 (11.13 eV). Charge transfer in the complexes is studied through natural population analysis and non-bonding interactions are evaluated through quantum theory of atoms in molecules (QTAIM) and non-covalent interaction analyses. These complexes have absorption maxima (1076–1486 nm) in the near-infrared region (NIR) and they are transparent in the UV region. The first hyperpolarizability of complex C is 1.7 × 10 7 au, which is much higher than the value of 3.7 × 10 4 au for a pure Li 3 O superalkali-doped B 12 N 12 complex calculated at the same level of theory, as reported by Sun et al. ( Dalton Trans. , 2016, 45 , 7500–7509). The large second hyperpolarizability values also reflect the enhanced nonlinear optical response. The best computed values for the electro-optical Pockels effect, second harmonic generation, and hyper-Rayleigh scattering are 3.29 × 10 10 au, 1.17 × 10 10 au, and 6.71 × 10 6 au, respectively. Furthermore, the electro-optic dc-Kerr effect and electric-field-induced second harmonic generation have maximum values of 3.96 × 10 11 au and 3.46 × 10 10 au at 1064 nm. There are enhancements in the quadratic nonlinear refractive index ( n 2 ) values for complexes A–G, with a highest n 2 value of 3.35 × 10 −8 cm 2 W −1 at 1064 nm. These results suggest that mixed-superalkali-doped B 12 N 12 nanoclusters are potential candidates when designing high-performance NLO materials.
Type of Medium:
Online Resource
ISSN:
1477-9226
,
1477-9234
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2022
detail.hit.zdb_id:
2001339-5
detail.hit.zdb_id:
1472887-4
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