ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
We theoretically investigate the internal rotations of the methyl group in methyl-azabenzenes, such as o- and m-methylpyridines, 2-methylpyrazine, 4-methylpyrimidine, 4-methylpyridadine, and 4-methyl-1,2,3-triazine in the ground, excited, and anionic states. The calculated rotational barriers reproduce well the experimental data. Orbital pictures are given for the barrier changes by excitation and electron attachment. An idea of π*–σ* hyperconjugation is applied for a comprehensive interpretation of the barrier changes. A correlation is found between the rotational barriers and the splitting of the lowest and next-lowest unoccupied molecular orbitals. © 2001 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1364677
