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Su ve Benzen Çözeltilerinde 5,5-Dimetil-1-Pirolin N-Oksit'in Bazı Radikal Ürünlerinin Teorik İnce Yapı Çiftlenim Sabitleri

Theoretical Hyperfine Coupling Constants of Some Radical Adducts to 5,5-Dimethyl-1-Pyrroline N-Oxide in Water and Benzene Solutions

Journal Name:

  • Süleyman Demirel Üniversitesi Fen Dergisi

Publication Year:

  • 2016

Key Words:

Keywords (Original Language):

Author NameUniversity of AuthorFaculty of Author
Abstract (2. Language): 
The ground state optimized structures of some radical adducts of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in water and benzene solutions have been determined by using Density Functional Theory (DFT/B3LYP, DFT/B3PW91 ve DFT/PBEPBE) ve Hartree Fock (HF) methods with 6-31G (d,p), 6-311++G (d,p), LanL2DZ, LanL2MB and SDD levels. As trapped radicals, H, OH, O(CH2)(CH3) and OC(CH3)3 have been used. The calculated isotropic hyperfine coupling constants of all the trapped radicals have been seen to be agree with the corresponding experimental data. The hyperfine coupling constant due to the fi proton of nitroxide radical is concluded to be effected with the opposite spin density of oxygen nucleus bonded to the nitrogen. From all the calculated data it was obtained that on the hyperfine calculations the DFT (B3LYP) LANL2MB level is superior relative to the other levels for the used radicals. Also, the study has been enriched by the computational of the geometrical parameters, binding energies, atomic spin densities and hyper conjugative interaction energies for all the radical adducts.
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Abstract (Original Language): 
Su ve benzen çözeltilerinde 5,5-dimetil-1-pirolin N-oksit (DMPO)'nun bazı radikal ürünlerinin temel hal optimize yapıları, 6-31G (d,p), 6-311++G (d,p), LanL2DZ, LanL2MB ve SDD setlerinde Yoğunluk Fonksiyon Teori (DFT/B3LYP, DFT/B3PW91 ve DFT/PBEPBE) ve Hartree Fock (HF) metotları kullanılarak hesaplandı. Tuzaklanmış radikaller olarak, H, OH, O(CH2)(CH3) ve OC(CH3)3 kullanıldı. Tuzaklanan radikallerin hesaplanan izotropik ince yapı çiftlenim sabitlerinin, deneysel veriler uyum içinde olduğu görüldü. Azot radikalinin fi protonundan kaynaklı aşırı ince yapı çiftlenim sabitinin, azota bağlı oksijen çekirdeğindeki zıt spin yoğunluğundan etkilendiği görüldü. Elde edilen bütün teorik sonuçlardan, kullanılan radikaller için ince yapı hesaplamalarında, DFT(B3LYP)/LANL2MB setinin diğer setlere kıyasla deneysel veriler ile daha uyumlu sonuçlar verdiği tespit edildi. Ayrıca çalışma, bütün radikal ürünleri için teorik geometrik parametreler, bağlanma enerjileri, atomik spin yoğunlukları ve hiper konjugatif etkileşim enerjileri ile zenginleştirildi.
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