Premium
Next‐generation quantum theory of atoms in molecules for the photochemical ring‐opening reactions of oxirane
Author(s) -
Bin Xin,
Azizi Alireza,
Xu Tianlv,
Kirk Steven R.,
Filatov Michael,
Jenkins Samantha
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25957
Subject(s) - conical intersection , chemistry , planarity testing , ring (chemistry) , molecule , traverse , quantum , torsion (gastropod) , atoms in molecules , photochemistry , crystallography , computational chemistry , geometry , molecular physics , physics , quantum mechanics , medicine , surgery , mathematics , organic chemistry , geodesy , geography
The conical intersections corresponding to the C─O and C─C ring opening were optimized and the reaction paths traversing these intersections were obtained. Investigation of the C─O ring opening revealed that when traversing the lowest energy conical intersection, the reaction path returns to the closed ring geometry. The C─O path traversing the intersection featuring torsion of terminal CH 2 group however, led to a ring‐opened geometry, an H‐shift and the formation of acetaldehyde that can undergo further dissociation. The observation of different reaction paths was explained by the 3‐D paths from quantum theory of atoms in molecules (QTAIM) that defined the most preferred direction of electronic motion that precisely tracked the mechanisms of bond breaking and formation throughout the photo‐reactions. The size, orientation, and location of these most preferred 3‐D paths indicated the extent and direction of motion of atoms, bonds, and the degree of torsion or planarity of a bond indicating a predictive ability.