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<p>The impact of single scandium atom substitution doping on the structural, electronic, and nonlinear optical properties of 13 compositionally diverse X<sub>12</sub>Y<sub>12</sub> nanocages were systematically investigated using density functional theory. Sc doping induces significant local structural distortions in the high-symmetry pristine cage architectures, quantified through changes in bond lengths (up to 0.51 <i>Å</i> elongation) and bond angles (up to 22.47° deviation), with the most pronounced effects observed in non-metallic clusters including B<sub>12</sub>P<sub>12</sub>, B<sub>12</sub>N<sub>12</sub>, and C<sub>24</sub>. Comprehensive electronic descriptor analysis reveals that Sc doping universally enhances electron-donating capacity via reduced ionization potential (average reduction of 3.1 <i>eV</i> across all systems), but generally reduces kinetic stability (higher chemical reactivity), as evidenced by significant narrowing of the HOMO-LUMO gap (<i>E</i><sub><i>g</i></sub>) and decreased chemical hardness (<i>η</i>) for 11 of 13 systems, while all Sc substitution reactions are thermodynamically feasible with negative substitution energies. Notable exceptions to this destabilization trend include C<sub>23</sub>Sc (slightly increased <i>E</i><sub><i>g</i></sub><i>/η</i>) and Ge<sub>11</sub>ScC<sub>12</sub> (unchanged <i>E</i><sub><i>g</i></sub><i>/η</i>), which exhibit robust structural resilience against dopant-induced perturbation. Sc substitution breaks the centrosymmetry of all pristine clusters, generating substantial electric dipole moments (<i>µ</i>, 1.2 ~ 8.7 <i>D</i>) and altering molecular electrostatic potential distributions, with Sc acting as either a positive electron-deficient or negative/neutral electron-rich potential center depending on host lattice electronegativity. Crucially, while the effect on linear polarizability (<i>α</i>) is system-dependent (ranging from 87% reduction to 372% enhancement), Sc doping universally and dramatically enhances the static first hyperpolarizability (<i>β</i><sub><i>0</i></sub>) by 3 ~ 6 orders of magnitude for all investigated nanocages. Exceptionally high <i>β</i><sub><i>0</i></sub> values exceeding 100,000 <i>a.u.</i> are achieved in seven systems. This extraordinary second-order NLO response enhancement is quantitatively attributed to the synergistic effects of reduced transition energy (<i>ΔE</i>, dominant contribution, 60 ~ 85% of <i>β</i><sub><i>0</i></sub> variation), increased dipole moment difference between ground and excited states (<i>Δµ</i>, 10 ~ 25% contribution), and enhanced oscillator strength (<i>f</i><sub><i>0</i></sub>, 5 ~ 15% contribution). The findings establish single-atom Sc doping as a highly potent strategy for engineering X<sub>12</sub>Y<sub>12</sub> nanocages with tailored high-performance NLO properties for advanced optoelectronic and photonic applications, despite the associated trade-off in kinetic stability for most compositions.</p>

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Sc-Induced Modulation of Structural Distortion, Chemical Stability Trade-Off, and Nonlinear Optical Response in X12Y12 (X = B, Al, C, Si, Ge, Li, Zn, Cd, Pb, Sb, Bi, Cu; Y = N, P, O, F, Cl) Nanocages: a DFT Perspective

  • 期刊论文

  • 发表日期：

    2026年7月22日

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  • Jian Zhang,
  • Jing Liu,
  • Shuangtao Pan

摘要

The impact of single scandium atom substitution doping on the structural, electronic, and nonlinear optical properties of 13 compositionally diverse X12Y12 nanocages were systematically investigated using density functional theory. Sc doping induces significant local structural distortions in the high-symmetry pristine cage architectures, quantified through changes in bond lengths (up to 0.51 Å elongation) and bond angles (up to 22.47° deviation), with the most pronounced effects observed in non-metallic clusters including B12P12, B12N12, and C24. Comprehensive electronic descriptor analysis reveals that Sc doping universally enhances electron-donating capacity via reduced ionization potential (average reduction of 3.1 eV across all systems), but generally reduces kinetic stability (higher chemical reactivity), as evidenced by significant narrowing of the HOMO-LUMO gap (Eg) and decreased chemical hardness (η) for 11 of 13 systems, while all Sc substitution reactions are thermodynamically feasible with negative substitution energies. Notable exceptions to this destabilization trend include C23Sc (slightly increased Eg/η) and Ge11ScC12 (unchanged Eg/η), which exhibit robust structural resilience against dopant-induced perturbation. Sc substitution breaks the centrosymmetry of all pristine clusters, generating substantial electric dipole moments (µ, 1.2 ~ 8.7 D) and altering molecular electrostatic potential distributions, with Sc acting as either a positive electron-deficient or negative/neutral electron-rich potential center depending on host lattice electronegativity. Crucially, while the effect on linear polarizability (α) is system-dependent (ranging from 87% reduction to 372% enhancement), Sc doping universally and dramatically enhances the static first hyperpolarizability (β0) by 3 ~ 6 orders of magnitude for all investigated nanocages. Exceptionally high β0 values exceeding 100,000 a.u. are achieved in seven systems. This extraordinary second-order NLO response enhancement is quantitatively attributed to the synergistic effects of reduced transition energy (ΔE, dominant contribution, 60 ~ 85% of β0 variation), increased dipole moment difference between ground and excited states (Δµ, 10 ~ 25% contribution), and enhanced oscillator strength (f0, 5 ~ 15% contribution). The findings establish single-atom Sc doping as a highly potent strategy for engineering X12Y12 nanocages with tailored high-performance NLO properties for advanced optoelectronic and photonic applications, despite the associated trade-off in kinetic stability for most compositions.