Abstract
Highly correlated ab initio molecular orbital methodologies have been used in the study of substituent effects on the singlet-triplet gaps of a series of nitrenium ions and their corresponding isoelectronic carbenes. Calculations in solution were carried out with the isodensity polarizable continuum models, IPCM. The results show a net stabilization of the singlet species as a result of electronic density donation of the substituents to a vacant p orbital located in the central atom. It is shown that this "π-donor-π-acceptor" dependence of the singlet-triplet gap is more significant in the case of the nitrenium ions, due to the presence of a positive charge. In addition, it was found that the singlet-triplet gaps decrease with the polarity of the solvent, most likely due to stabilizing electrostatic interactions between the solvent and the charge distribution of the singlet.
Original language | English (US) |
---|---|
Pages (from-to) | 2732-2738 |
Number of pages | 7 |
Journal | Journal of Physical Chemistry A |
Volume | 102 |
Issue number | 16 |
DOIs | |
State | Published - Apr 16 1998 |
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry