Spin-orbit effects on the Sn-119 magnetic-shielding tensor in solids: a ZORA/DFT investigation
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, cilt.18, sa.28, ss.18914-18922, 2016 (SCI-Expanded)
- Yayın Türü: Makale / Tam Makale
- Cilt numarası: 18 Sayı: 28
- Basım Tarihi: 2016
- Doi Numarası: 10.1039/c6cp03807g
- Dergi Adı: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
- Sayfa Sayıları: ss.18914-18922
- Abdullah Gül Üniversitesi Adresli: Hayır
Özet
Periodic-boundary and cluster calculations of the magnetic-shielding tensors of Sn-119 sites in various co-ordination and stereochemical environments are reported. The results indicate a significant difference between the predicted NMR chemical shifts for tin(II) sites that exhibit stereochemically-active lone pairs and tin(IV) sites that do not have stereochemically-active lone pairs. The predicted magnetic shieldings determined either with the cluster model treated with the ZORA/Scalar Hamiltonian or with the GIPAW formalism are dependent on the oxidation state and the co-ordination geometry of the tin atom. The inclusion of relativistic effects at the spin-orbit level removes systematic differences in computed magnetic-shielding parameters between tin sites of differing stereochemistries, and brings computed NMR shielding parameters into significant agreement with experimentally-determined chemical-shift principal values. Slight improvement in agreement with experiment is noted in calculations using hybrid exchangecorrelation functionals.