Role of electronic curve crossing of benzene <i>S</i>₁ state in the photodissociation of aryl halides, effect of fluorination: RASSI‐SO MS‐CASPT2 study

Abstract

Abstract An ab initio study of the role of electronic curve crossing of benzene S 1 state in the photo dissociation dynamics of the iodobenzene and effect of fluorination is presented. Two dissociative life times observed in iodobenzene is attributed to the coupled repulsive potential energy curves of the low‐lying n −σ*, π−σ*, π−π* states. The direct channel is attributed to the alkyl like transition and the indirect channel is attributed to the mixing of the alkyl like transitions with the low lying benzene π−π* transitions. Fluorination of iodobenzene results in a substantial increase in the direct channel product. To analyze the possible role of electronic curve crossing of these transitions, potential energy curves of low‐lying n −σ*, π−σ*, π−π* states were studied including spin‐orbit and relativistic effects using the Restricted Active Space state interaction multistate complete active space perturbation theory (RASSI‐MS‐CASPT2) method. Crossing behavior of spin‐free and spin‐orbit potential energy curves was analyzed for the role of the benzene S 1 state. Our results indicate the curve crossing region to be around 2.00–2.35 Å for both C 6 H 5 I and C 6 F 5 I. Analysis of effect of fluorination on the energies of states corresponding to benzene π−π* and n −σ* transitions suggests an increase in the energy of benzene π−π* states and a decrease in the energy of the states corresponding to n −σ* transitions. Increased spin‐orbit gap, increased separation of the benzene S 1 (π−π*) state and n −σ* states in the region of curve crossing, lesser mixing of the π−π* and n −σ* states, an order of magnitude decrease in the transition strength to the benzene singlet transition all contributed to the observed substantial increase in the quantum yield of the direct channel product on fluorination of aryl halides. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009