title: Isomerization around a C=N double bond and a C=C double bond with a nitrogen atom attached: thermal and photochemical routes.
abstract: The Longuet-Higgins phase change theorem is used to show that, in certain photochemical reactions, a single product is formed via a conical intersection. The cis-trans isomerization around the double bond in the formaldiminium cation and vinylamine are shown to be possible examples. This situation is expected to hold when the reactant can be converted to the product via two distinct elementary ground-state reactions that differ in their phase characteristics. In one, the total electronic wavefunction preserves its phase in the reaction; in the other, the phase is inverted. Under these conditions, a conical intersection necessarily connects the first electronic excited state to the ground state, leading to rapid photochemical isomerization following optical excitation. Detailed quantum chemical calculations support the proposed model. The possibility that a similar mechanism is operative in other systems, among them the rapid photo-induced cis-trans isomerization of longer protonated Schiff bases (the parent chromophores of rhodopsins), is discussed.
authors.affiliation: Department of Physical Chemistry, Farkas Center for Light Induced Processes, The Hebrew University of Jerusalem, Givat Ram, Jerusalem 91904, Israel.
authors.forename: Shmuel
authors.initials: S
authors.lastname: Zilberg
authors.forename: Yehuda
authors.initials: Y
authors.lastname: Haas