Su ve Benzen Çözeltilerinde 5,5-Dimetil-1-Pirolin N-Oksit’in Bazi Radikal Ürünlerinin Teorik Ince Yapi Çiftlenim Sabitleri
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Tarih
2016
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Süleyman Demirel Üniversitesi
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Su ve benzen çözeltilerinde5,5-dimetil-1-pirolin N-oksit(DMPO)’nun bazi radikal ürünlerinin temel hal optimize yapilari, 6-31G (d,p),6-311++G (d,p), LanL2DZ, LanL2MB ve SDD setlerinde Yogunluk Fonksiyon Teori (DFT/B3LYP,DFT/B3PW91 ve DFT/PBEPBE) ve Hartree Fock (HF) metotlari kullanilarakhesaplandi. Tuzaklanmis radikaller olarak, H, OH, O(CH2)(CH3) ve OC(CH3)3 kullanildi.Tuzaklanan radikallerin hesaplanan izotropik ince yapi çiftlenim sabitlerinin,deneysel veriler uyum içinde oldugu görüldü. Azot radikalinin ß protonundan kaynakli asiri ince yapiçiftlenim sabitinin, azota bagli oksijen çekirdegindeki zit spin yogunlugundanetkilendigi görüldü. Elde edilen bütün teorik sonuçlardan, kullanilan radikalleriçin ince yapi hesaplamalarinda, DFT(B3LYP)/LANL2MB setinin diger setlere kiyasladeneysel veriler ile daha uyumlu sonuçlar verdigi tespit edildi. Ayricaçalisma, bütün radikal ürünleri için teorik geometrik parametreler, baglanmaenerjileri, atomik spin yogunluklari ve hiper konjugatif etkilesim enerjileriile zenginlestirildi.
The groundstate optimized structures of some radical adducts of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in water and benzenesolutions 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 isotropichyperfine coupling constants of all the trapped radicals have been seen to beagree with the corresponding experimental data. The hyperfine coupling constantdue to the ß proton of nitroxideradical is concluded to be effected with the opposite spin density of oxygennucleus bonded to the nitrogen. From all the calculated data it was obtainedthat on the hyperfine calculations the DFT (B3LYP) LANL2MB level is superiorrelative to the other levels for the used radicals. Also, the study has beenenriched by the computational of the geometrical parameters, binding energies,atomic spin densities and hyper conjugative interaction energies for all theradical adducts.
The groundstate optimized structures of some radical adducts of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in water and benzenesolutions 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 isotropichyperfine coupling constants of all the trapped radicals have been seen to beagree with the corresponding experimental data. The hyperfine coupling constantdue to the ß proton of nitroxideradical is concluded to be effected with the opposite spin density of oxygennucleus bonded to the nitrogen. From all the calculated data it was obtainedthat on the hyperfine calculations the DFT (B3LYP) LANL2MB level is superiorrelative to the other levels for the used radicals. Also, the study has beenenriched by the computational of the geometrical parameters, binding energies,atomic spin densities and hyper conjugative interaction energies for all theradical adducts.
Açıklama
Anahtar Kelimeler
Asiri ince yapi sabiti, DMPO, radikal, ESR, DFT
Kaynak
Süleyman Demirel University Faculty of Arts and Science Journal of Science
WoS Q Değeri
Scopus Q Değeri
Cilt
11
Sayı
2
