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Title:Bond Dissociation Energies Of Diatomic Lanthanide Sulfides And Selenides
Author(s):Sorensen, Jason J
Contributor(s):Morse, Michael D.; Tieu, Erick
Subject(s):Photodissociation and photochemistry
Abstract:Bond dissociation energies pose a major challenge for modern computational methods. This is largely due to the need to treat electron correlation to the same level of accuracy in the molecule as in the separated atoms. This becomes especially difficult in transition metal and lanthanide containing species, as the electronic state densities are particularly high. As important as this issue is, the problem has been largely unassailable due to a long-standing dearth of highly accurate experimental data that is suitable for use as computational benchmarks. In this study, we use the sharp onset of predissociation in a highly congested, quasicontinuous optical spectrum to precisely measure the bond dissociation energies of 10 diatomic lanthanide sulfides, LnS, along with the corresponding lanthanide selenides, LnSe. These studies provide lanthanide thermochemistry of unparalleled accuracy, while also providing an opportunity to analyze the bonding in terms of the separated atom states to which the ground states diabatically correlate. From this analysis, it is proposed that most of the LnS and LnSe molecules diabatically correlate to the Ln$^{+}$ (4f$^{N}$ 5d$^{1}$) + S$^{-}$(3s$^{2}$ 3p$^{5}$)/ Se$^{-}$(4s$^{2}$ 4p$^{5}$) separated ion limit. Our previous observation that the bond dissociation energies of the diatomic transition metal sulfides are universally about 15\% stronger than their selenide analogs is extended to these 10 LnS/LnSe molecules, and the trend is observed to hold.
Issue Date:2021-06-25
Publisher:International Symposium on Molecular Spectroscopy
Genre:Conference Paper / Presentation
Date Available in IDEALS:2021-09-24

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