THERMAL CHEMISTRY AS AN EXERCISE IN PHOTOCHEMISTRY

The Linear Combination of Fragment Configurations approach is used to generate qualitative potential energy surfaces. The theory is applied to “forbidden” cycloadditions, solvolysis, and electrophilic aromatic substitution. It is also used to illuminate principles of chemical selectivity and the electronic structure of diradicals. It is argued that chemical intermediates in thermal reactions arise from excite surfaces under the influence of perturbations such as substituent effects and solvation. © IUPAC