On the problem of theoretical evaluation of the rotational barrier in aromatics with adjacent conjugated group: benzaldehyde and N-methylbenzamide

Autor:	Eckhard Koglin, Robert J. Meier
Rok vydání:	2002
Předmět:	Benzaldehyde Bond length chemistry.chemical_compound Molecular geometry Chemistry Computational chemistry Aryl Substituent General Physics and Astronomy Molecule Physical and Theoretical Chemistry Benzene Ring (chemistry)
Zdroj:	Chemical Physics Letters. 353:239-243
ISSN:	0009-2614
DOI:	10.1016/s0009-2614(02)00032-5
Popis:	The rotational barrier in benzaldehyde was evaluated using DFT methods and CCSD. Compared to experimental values, the calculated values are typically a factor 2 too high. Evidence is provided this also applies to N -methylbenzamide. The results once more suggest that molecules comprising a benzene ring with a π-conjugated substituent form a special problem with respect to calculation of the rotational barrier around the C(sp2)–C(aryl) bond. It must be concluded that current DFT functionals cannot properly handle such barriers. Conversely, successfully describing these rotational barriers may be an appropriate and stringent test for new functionals.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::4c29e2d73046a6fcc37d85252cb5cf08 https://doi.org/10.1016/s0009-2614(02)00032-5 Zobrazit plný text záznamu Full Text from ScienceDirect