Kocakaya, Safak OezhanPirinccioglu, Necmettin2024-04-242024-04-2420101300-0527https://doi.org/10.3906/kim-0909-272https://search.trdizin.gov.tr/yayin/detay/103282https://hdl.handle.net/11468/19352The 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 Moller-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 nitroso group 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 on the transition state. The MP2 method produces better and comparable results with the few available experimental values.eninfo:eu-repo/semantics/openAccessPara-Substituted NitrosobenzenesC-N Bond RotationPolar Substituent EffectMolecular Modelling DftMp2PcmA 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 calculationsA 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 calculationsArticle343399410WOS:00027989360000910328210.3906/kim-0909-272Q3