Göcen T., Bayarı S.
NANOMATERIALS, cilt.16, sa.21, ss.1349-1372, 2026 (SCI-Expanded, Scopus)
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Yayın Türü:
Makale / Tam Makale
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Cilt numarası:
16
Sayı:
21
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Basım Tarihi:
2026
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Doi Numarası:
10.3390/nano16211349
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Dergi Adı:
NANOMATERIALS
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Derginin Tarandığı İndeksler:
Academic Search Ultimate (EBSCO), Natural Science Collection (ProQuest), Biological Science Database (ProQuest), Engineering Source (EBSCO), Scopus, Materials Science & Engineering Collection (ProQuest), Technology Collection (ProQuest), Science Citation Index Expanded (SCI-EXPANDED), Chemical Abstracts Core, INSPEC, Directory of Open Access Journals
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Sayfa Sayıları:
ss.1349-1372
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Hacettepe Üniversitesi Adresli:
Evet
Özet
Endohedral nitrogen fullerenes are promising candidates for molecular spin qubits and quantum sensing. We compare nitrogen spin localization and N···C contact topology in N@C60 and N@C70. Baseline structural, vibrational, electronic, population, spin density, noncovalent interaction (NCI), and quantum theory of atoms in molecules (QTAIM) analyses used UB3LYP/6-31G(d). Counterpoise-corrected interaction energies were calculated using UB3LYP-D3(BJ)/def2-TZVP, with def2-QZVP checks. QTAIM sensitivity was assessed at fixed geometries using UB3LYP/def2-TZVP and UωB97X-D/def2-TZVP. Encapsulation leaves both cages essentially unperturbed: selected vibrational shifts are ≤0.8 cm−1 and HOMO–LUMO gap changes are ≤0.007 eV. Frontier orbitals remain cage-dominated, whereas Mulliken and Hirshfeld analyses assign 94–99% of the spin population to nitrogen, without substantial charge transfer. Counterpoise-corrected def2-TZVP interaction energies are −9.09 and −8.55 kcal mol−1, respectively; def2-QZVP changes each by <0.05 kcal mol−1. NCI/QTAIM descriptors indicate weak, low-density N···C contacts. N@C60 retains 60 connections across all three tested levels; N@C70 has eight at baseline and the same six in both def2-TZVP calculations. Thus, extensive and restricted contact networks remain distinct, although the exact N@C70 count and local descriptors depend on computational level. Predominantly nitrogen-centered spin therefore accompanies different surrounding contact topologies in cages that differ in size and shape.