Internal conversion induced by external electric and magnetic fields

Abstract

We have developed a new methodology for calculating contributions to the rate constants (kIC) of internal conversion that are induced by external electric (kIC-E) or magnetic (kIC-M) fields.

Molecular phosphorescence enhancement by the plasmon field of metal nanoparticles

“…1,79,80 The k IC (S 1 → S 0 ) rate constant can also change. 64 Expressions describing such changes can be derived using second-order perturbation theory, where NACME and p⃑ or only p⃑ is the perturbation operator. 64,65 p⃑ is the electric dipole transition moment.…”

“…64 Expressions describing such changes can be derived using second-order perturbation theory, where NACME and p⃑ or only p⃑ is the perturbation operator. 64,65 p⃑ is the electric dipole transition moment. Changes in the IC rate constant can be more than one order of magnitude but occur only at very strong electrical fields of 10 9 –10 11 V m −1 , whereas changes in the k ISC (S 1 → T 1 ) rate constant occur only when the molecule is very close to the NP surface.…”

“…The k IC (S 1 → S 0 ) rate constant can also increase due to the external electric field 64,65 leading to the changes in k̆ IC (T̃ 1 → S̃ 0 ). In this work, we have estimated this effect on Rh123 and Rh123-2Br .…”

“…The (NACME + p⃑ ) operator is used as the perturbation operator in the second-order perturbation theory expression. 64 Thus, we neglect changes in k IC (S 1 → S 0 ) and in k̆ IC (T̃ 1 → S̃ 0 ).…”

“…The plasmon field affects the probability of radiative transitions, 56 and can also affect the rate constants of nonradiative transitions. 64,65 We are not aware of any implementation of theoretical models, which considers the plasmon field effect on the total lifetime of the molecular triplet state using computational methods that accounts for properties of the individual molecules. Here, we have developed such a computational method and applied it to the well-known xanthene dyes rhodamine 123 ( Rh123 ) and 2Br-rhodamine 123 ( Rh123-2Br ).…”