Solvation shift of a conical intersection in clusters of excited tetrakis(dimethyl amino)ethylene with ammonia and acetonitrile molecules

S. Sorgues (1) , J. M. Mestdagh (2) , B. Soep (2)

1 LCPO - Laboratoire de Chimie Physique D'Orsay
2 LFP - URA 2453 - Laboratoire Francis PERRIN

A supersonic expansion of the title molecule (TDMAE) with helium and polar solvent molecules S (ammonia or acetonitrile) generates TDAME(S)10 clusters. By applying the femtosecond pump–probe technique, a wavepacket is launched on the S1 potential energy surface of TDMAE. The electronic configuration of TDMAE changes from valence V(ππ*) to Zwitterionic C+C− when the wavepacket passes in the vicinity of a conical intersection. While argon as solvent slows down this switch by an inertial effect, the present polar molecules move the conical intersection, reduce the length of the way to access it and accelerate the corresponding V-to-Z energy transfer.

Domaines: Chimie théorique et/ou physique

S. Sorgues, J. M. Mestdagh, B. Soep. Solvation shift of a conical intersection in clusters of excited tetrakis(dimethyl amino)ethylene with ammonia and acetonitrile molecules. Chemical Physics Letters, 2004, 399, pp.234-238. ⟨10.1016/j.cplett.2004.09.151⟩. ⟨hal-00084714⟩