Nonadiabatic photodissociation process using an optical near field.

We demonstrated the deposition of nanometric Zn dots using photodissociation with gas-phase diethylzinc and an optical near field under nonresonant conditions. To explain the experimental results, we proposed an exciton-phonon polariton model, and discuss the quantitative experimental dependence of the deposition rate on the optical power and photon energy based on photodissociation involving multiple-step excitation via molecular vibration modes. The physical basis of this process, which seems to violate the Franck-Condon principle, is the optically nonadiabatic excitation of the molecular vibration mode due to the steep spatial gradient of the optical near-field energy.