- Turkish Journal of Chemistry
- Vol: 34 Issue: 3
- A theoretical study of the effects of polar substitution on the activation barriers for internal rot...
A theoretical study of the effects of polar substitution on the activation barriers for internal rotation around the C-N bond in p-substituted nitrosobenzenes: comparison of DFT and MP2 calculations
Authors : Şafak Özhan Kocakaya And Necmettin Pirinççioğlu
Pages : 399-410
Doi:10.3906/sag-1205-27
View : 11 | Download : 6
Publication Date : 9999-12-31
Article Type : Makaleler
Abstract :The activation barriers for internal rotation around the C-N bond in p-substituted nitrosobenzenes were calculated using the density functional theory (DFT) and second-order Møller-Plesset (MP2) methods with the 6-31+g(d) basis set. The polarisable continuum model (PCM) was used to model the solvent effect. An explicit water molecule was also introduced to form a hydrogen bond with the nitrosogroup and its effect on the barrier was studied by DFT. The barriers were well-correlated with Hammett sigma+ rather than sigma values, meaning a strong resonance effect. The MP2 method produces better and comparable results with the few available experimental values.Keywords : Para-substituted nitrosobenzenes, C-N bond rotation, polar substituent effect, molecular modelling DFT, MP2, PCM.