Quantum physical states for describing photonic assisted chemical change: I. Torsional phenomenon at femtosecond time scale

Abstract

Femtosecond torsional relaxation processes experimentally detected and recently reported by Clark et al. (Nature Phys. 8,225 (2012)) are theoretically dissected with a Hilbert/Fock quantum physical (QP) framework incorporating entanglement of photon/matter base states overcoming standard semi-classic vibrational descriptions. The quantum analysis of a generic Z/E (cis/trans) isomerization in abstract QP terms shed light to fundamental roles played by photonic spin and excited electronic singlet coupled to triplet states. It is shown that one photon activation cannot elicit femtosecond phenomenon, while a two-photon pulse would do. Estimated time scales for the two-photon case indicate the process to lie between a slower than electronic Franck-Condon-like transition yet faster than (semi-classic) vibration relaxation ones.