کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5419043 | 1506965 | 2007 | 10 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Ab initio and DFT study of the molecular conformations and the thermochemistry of the CH2CHC(O)OONO2 (APAN) atmospheric molecule and of the CH2CHC(O)OO and CH2CHC(O)O radicals
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
چکیده انگلیسی
The molecular structures and conformational mobilities of the atmospheric peroxyacryloyl nitrate, CH2CHC(O)OONO2 (APAN) molecule and its radical decomposition products CH2CHC(O)OO and CH2CHC(O)O were studied by ab initio and density functional methods. The potential energy curves for the internal rotations were calculated using the B3LYP hybrid functional with the 6-311++G(d,p) basis set. The equilibrium conformation of APAN, determined at B3LYP/6-311++G(3df,3pd) level, is characterized by a structure in which groups of atoms adjacent to the peroxide bond lie in almost perpendicular planes, Ï(COON) = 86.4°. A quantum statistical analysis showed that only a 7% of the internal rotors of the above molecules can freely rotate at room temperature. From isodesmic energies calculated at the G3MP2//B3LYP/6-311++G(3df,3pd) level of theory, standard enthalpies of formation at 298 K for APAN, CH2CHC(O)OO and CH2CHC(O)O are predicted to be â34.8, â8.9, and â16.0 kcal molâ1. The resulting ON and OO bond dissociation enthalpies for the channels CH2CHC(O)OONO2 â CH2CHC(O)OO + NO2 and CH2CHC(O)OONO2 â CH2CHC(O)O + NO3 of 34.1 and 36.4 kcal molâ1 are significant larger than those reported for similar processes of the atmospherically relevant PAN species.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Structure: THEOCHEM - Volume 814, Issues 1â3, 15 July 2007, Pages 51-60
Journal: Journal of Molecular Structure: THEOCHEM - Volume 814, Issues 1â3, 15 July 2007, Pages 51-60
نویسندگان
MarÃa P. Badenes, Carlos J. Cobos,