The Dipole Correction Method for Extracting Excited State Potentials and Electronic Transition Dipoles from Fluorescence Data

Abstract

AbstractWe have developed a new inversion scheme for the accurate extraction of excited state potentials from fluorescence line positions and line strengths which does not make use of the Franck Condon Approximation (FCA). Our “dipole correction” method also enables the extraction of the coordinate dependence of the electronic transition dipoles. The accuracy of the potential energy surfaces (PES) thus extracted is much higher than that of the FCA‐ derived PES. The procedure, illustrated for the Na2 A(1Σ+u) → X(1Σ+g) P‐branch emission, results in global errors of 0.1 cm−1, and average errors near the PES minimum of 0.03 cm−1, with A → X electronic transition dipole function accuracies better than 1×10−3 Debye. We also show that it is possible to use emission data from a few select states: Global errors as small as 0.08 cm−1 for the Na2 B(1Πu) PES, using emissions data from only the s=0–5 low‐lying levels or the s=20–23 states, are demonstrated.