The Dipole Correction Method for Extracting Excited State Potentials and Electronic Transition Dipoles from Fluorescence Data |
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| Authors: | Xuan Li Moshe Shapiro |
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| Affiliation: | 1. Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T1Z1, Canada phone: +1 604 822-8374 fax: +1 604 822-2847;2. Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T1Z1, Canada phone: +1 604 822-8374 fax: +1 604 822-2847
Department of Chemical Physics, Weizmann Institute of Science, Rehovot, 76100, Israel |
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| Abstract: | We 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. |
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| Keywords: | electronic structure fluorescence spectroscopy |
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