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<p>In this research, optical and nonlinear optical (NLO) properties of benzocryptand doped with alkaline earth metals (Be, Mg, Ca) both exohedrally and endohedrally were studied using DFT. Nine combinations of doped metals BzC, i.e., A-BzC-A* (A, A* = Be, Mg, Ca), were analyzed. Excess electron doping effects on optical and electronic properties for NLO response were also explored. Frontier molecular orbitals (FMOs), density of states (DOS), absorption maxima (<i>λ</i><sub>max</sub>), and transition density matrix (TDM) analyses were conducted to investigate charge transfer phenomena. Parameters like dipole moment (<i>μ</i>), binding energy (<i>E</i><sub>b</sub>), interaction energy (<i>E</i><sub>int</sub>), electron affinity, excitation energy (ΔE), and natural bonding orbitals (NBO) were examined. Non-covalent interaction (NCI) and infrared (IR) analysis revealed weak interactions and vibrational frequencies. Enhanced <i>λ</i><sub>max</sub> (536-3200&#xa0;nm) and reduced band gap (0.34-2.71&#xa0;eV) were observed. Among all, the Ca-Ca*-doped BzC complex demonstrated the highest NLO response, with endohedral and exohedral Ca doping resulting in the most remarkable enhancement in hyperpolarizability, confirming the effectiveness of bimetallic positioning in enhancing NLO properties. Bimetallic doping notably improved linear polarizability (<i>α</i><sub>iso</sub>) and hyperpolarizability (<i>β</i><sub>tl</sub>), indicating potential for novel NLO materials. DFT and TD-DFT for all compounds’ quantum chemical simulations were conducted using Gaussian 09 with molecular geometries and orbitals visualized in Gauss View 6.0. Furthermore, physical and chemical parameters, including bond lengths, dihedral angles, dipole moments, and charge densities, were analyzed. All the newly designed complexes were optimized at the B3LYP/6-31G (d′, p′) level of theory.</p>

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Bimetallic doping of benzocryptand with alkaline earth metals for outstanding nonlinear optical response; a DFT study

  • 期刊论文

  • 发表日期：

    2025年6月5日

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  • Hillia Fatima,
  • Naima Rafique,
  • Muhammad Nouman,
  • Areeba Asif,
  • Noman Akhtar

摘要

In this research, optical and nonlinear optical (NLO) properties of benzocryptand doped with alkaline earth metals (Be, Mg, Ca) both exohedrally and endohedrally were studied using DFT. Nine combinations of doped metals BzC, i.e., A-BzC-A* (A, A* = Be, Mg, Ca), were analyzed. Excess electron doping effects on optical and electronic properties for NLO response were also explored. Frontier molecular orbitals (FMOs), density of states (DOS), absorption maxima (λmax), and transition density matrix (TDM) analyses were conducted to investigate charge transfer phenomena. Parameters like dipole moment (μ), binding energy (Eb), interaction energy (Eint), electron affinity, excitation energy (ΔE), and natural bonding orbitals (NBO) were examined. Non-covalent interaction (NCI) and infrared (IR) analysis revealed weak interactions and vibrational frequencies. Enhanced λmax (536-3200 nm) and reduced band gap (0.34-2.71 eV) were observed. Among all, the Ca-Ca*-doped BzC complex demonstrated the highest NLO response, with endohedral and exohedral Ca doping resulting in the most remarkable enhancement in hyperpolarizability, confirming the effectiveness of bimetallic positioning in enhancing NLO properties. Bimetallic doping notably improved linear polarizability (αiso) and hyperpolarizability (βtl), indicating potential for novel NLO materials. DFT and TD-DFT for all compounds’ quantum chemical simulations were conducted using Gaussian 09 with molecular geometries and orbitals visualized in Gauss View 6.0. Furthermore, physical and chemical parameters, including bond lengths, dihedral angles, dipole moments, and charge densities, were analyzed. All the newly designed complexes were optimized at the B3LYP/6-31G (d′, p′) level of theory.