کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5418776 | 1394394 | 2006 | 9 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Geometry, solvent, and polar effects on the relationship between calculated core-electron binding energy shifts (ÎCEBE) and Hammett substituent (Ï) constants
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
چکیده انگلیسی
According to Lindberg et al. there exists an equation ÎCEBE=ÎºÏ for substituted benzene derivatives. Core-electron binding energy shift (ÎCEBE) is the difference between the CEBE of a specific carbon in monosubstituted benzene derivatives (C6H5-Z) and in benzene (C6H5-H); κ is related to a reaction constant and Ï is the experimental Hammett substituent constant. The object of the present work is to investigate geometry, solvent, and polar effects on Lindberg's equation using theoretically calculated ÎCEBE. The CEBEs were calculated using DFT within the scheme ÎEKS (PW86x-PW91c/TZP+Crel). The geometry has only little effect on the CEBE values. A regression relation between ÎCEBE and Ï takes the form ÎCEBE=κÏâC with κâ
1.17 and Câ
0.17. We estimated 69 Ï constants in water that have not been presented in the literature. Theoretical resonance (ÏR) and inductive (ÏI) effects were calculated using Taft equations. ÎCEBE (R) and ÎCEBE (I) effects on ÎCEBE were also calculated using Taft-like equations. The quality of the correlation to the resonance is better than that to the inductive effect, in water. The regression quality in aqueous organic solvent is poorer than in water in both Lindberg and Taft equations. The solvent effect is greater on the resonance than on the inductive effect.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Structure: THEOCHEM - Volume 758, Issue 1, 16 January 2006, Pages 61-69
Journal: Journal of Molecular Structure: THEOCHEM - Volume 758, Issue 1, 16 January 2006, Pages 61-69
نویسندگان
Maximiliano Segala, Yuji Takahata, Delano P. Chong,