Theoretical study of the electronic structure of mono-bromide of lanthanum molecule including spin-orbit coupling effects

Hamade, Yaman; Taher, F.; Haidar, Yehya; Rhallabi, A.

doi:10.1007/s00894-019-4114-4

Cited by 2 publications

(4 citation statements)

References 19 publications

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“…The calculated geometry parameters, vibrational frequencies, and BDEs are given in Table with the components for calculating the BDEs in the Supporting Information. The calculated bond distances and harmonic vibrational frequencies are in good agreement with the available experimental data − and prior computational studies. ,− Our calculated bond lengths are within <1 pm of the experimental values, and the calculated ω e values are within 5 cm –1 of the experiment. ,− , Additional high-level CCSD(T) and multireference configuration interaction (MRCI) calculations of the ω e for ScCl, ScBr, and LaCl are consistent with our results.…”

Section: Resultssupporting

confidence: 88%

“… a Reference (theory, CISD/CPF). b Reference (theory, MRCI + outer core + first-order DK). c Reference (theory, CCSDT/CBS). d Reference (theory, MRCI/RCCSD(T)). e Reference (theory, CASSCF/MRCI). f Reference (theory, CASSCF/MRCI). g Reference (theory, CASSCF/MRCI). h Reference (theory, CASSCF/MRCI). i Reference (theory, MCPF). j Reference (theory, CAS-SCF/MRCI). k Reference (theory, DFT). l Reference (theory, DFT). m Reference (theory, CASSCF/MRCI). n Reference (theory, CAS-SCF/MRCI). o Reference (theory, CASSCF/MRCI). p Reference (theory, CASSCF/MRCI). q Reference (theory, CASSCF/MRCI). r Reference (theory, CASSCF/MRCI). s Reference (experimental compilation). t Reference (near IR Fluor). u Reference (Fluor exc IR). v Reference (microwave spectra, estimate D e = ω e 2 /4ω e χ e ). w Reference (mass spectrometry, M + BaF = MF + Ba, M + MF 2 = 2 MF). x Reference (experimental compilation). y Reference (mass spectrometry at 298 K). z Reference (estimated values). …”

Section: Resultsmentioning

confidence: 99%

“…We consider the chemiluminescent emission characterizing 16 reactions of the group 3 metals Sc, Y, and La and their dimers with F 2 , ClF, and Cl 2 as well as SF 6 ; Sc with Br 2 and ICl; Y with Br 2 and IBr; and Sc 2 and Y 2 with Cl and Br atoms. The available spectroscopic data from experiments ,,,,− ,− and calculations ,,− ,− ,− ,− are given in Tables – .…”

Section: Resultsmentioning

confidence: 99%

“… a Reference (theory, CASSCF/MRCI). b Reference (theory, CASSCF/MRCI). c Reference (theory, CASSCF/MRCI). d Reference (theory, CASSCF/MRCI). e T 0 . f Labeled c 1 3 Δ 1 in reference. g Assigned originally as B 1 Π. …”

Section: Resultsmentioning

confidence: 99%

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Observation of Selectively Populated Monohalide Excited States from the Reactions of Group 3 Metal (Sc, Y, and La) Monomers and Dimers with Halogen-Containing Molecules

et al. 2022

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The chemiluminescent reactions of the group 3 metals Sc and Y with F 2 , Cl 2 , Br 2 , ClF, ICl (Sc), IBr (Y), and SF 6 and La with F 2 , SF 6 , Cl 2 , and ClF have been studied at low pressures (6 × 10 −6 to 4 × 10 −4 Torr) using a beam-gas arrangement and extended to the 10 −3 Torr multiple collision pressure range. Contrary to previous reports, the observed chemiluminescent spectra are primarily attributed to emission from the metal monohalides. Extensive pressure and temperature dependence studies and high-level correlated molecular orbital theory calculations of the bond dissociation energies support this conclusion and the attribution of the chemiluminescence. Evidence for the "selective" production of a monohalide excited electronic state is obtained for several of the Sc and Y reactions. All reactions producing the metal monofluorides are first order with respect to the oxidant, while reactions producing the monochlorides and monobromides are found to be "faster than first order" with respect to the oxidant. This difference is associated with the metal halide bond dissociation energies and the metal halide product internal density of states. Analysis of the temperature dependence for six representative reactions indicates that the "selective" excited-state formation of the metal monohalides proceeds via a direct mechanism with negligible activation energy. We compare and contrast the present results with previous experiments and interpretations which have assigned the selective emission from these systems to the group 3 dihalides produced in a two-step reaction sequence analogous to an electron jump process. The current results suggest a distinctly different interpretation of the observed processes in these systems. The observed selectivity observed in these studies is remarkable given the significant number of known and potential excited states in the scandium and yttrium halides as well as their different electronic configurations.

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