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Microwave spectrum and molecular structure calculations for η4-butadiene ruthenium tricarbonyl.

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Title: Microwave spectrum and molecular structure calculations for η4-butadiene ruthenium tricarbonyl.
Authors: Daly, Adam M.1 (AUTHOR), Roehling, Kristen K.1 (AUTHOR), Hill, Rhett P.1 (AUTHOR), Gonzalez, Myla G.1 (AUTHOR), Kang, Xin2 (AUTHOR), McElwee-White, Lisa2 (AUTHOR), Kukolich, Stephen G.1 (AUTHOR) kukolich@arizona.edu
Source: Journal of Molecular Spectroscopy. Oct2024, Vol. 405, pN.PAG-N.PAG. 1p.
Subjects: Hyperfine coupling, Hyperfine structure, Molecular spectra, Nuclear structure, Molecular structure, Microwave spectroscopy
Abstract: [Display omitted] • First microwave spectrum measurements for the butadiene ruthenium tricarbonyl complex. • Extensive high level calculations on the molecular structure and nuclear quadrupole coupling for this complex. • First resolved and analysed 101Ru and 99Ru quadrupole coupling spectra in a molecule. • Core potential (ECP) basis sets give better structures; all-electron basis sets give better quadrupole calculations. The microwave spectrum of η4-butadiene ruthenium tricarbonyl was measured in the 5–15 GHz frequency range using a Flygare-Balle type pulsed beam Fourier transform microwave (FTMW) spectrometer. The rotational constants for the 102Ru isotopologue were determined to have the following values: A = 932.20099(42), B = 858.03248(47) and C = 831.35161(37) MHz. The centrifugal distortion constant d J is 0.0862(29)kHz. 22 a-dipole and 4c-dipole transitions were measured. Extensive high-level G16 calculations were made using DFT and MP2 methods with various basis sets, some including core-potentials (ECP). The best structure was calculated with Gaussian 16 using B3LYP/def2-QZVPP, which includes a core potential (ECP). Extensive all-electron calculations were made based on the best ECP structure to predict 101Ru and 99Ru quadrupole coupling strengths. Quadrupole hyperfine structure splittings were measured for both 101Ru and 99Ru. The hyperfine structure splittings for the 101Ru nuclear quadrupole were measured, yielding the values of 1.5χ aa = 98.12(17) MHz and 0.25(χ bb -χ cc) = 36.059(30). Measured hyperfine structure splittings for 99Ru quadrupole coupling yielded the values of 1.5χ aa = 16.99(77) MHz and 0.25(χ bb -χ cc) = 6.23(32). These values are in reasonable agreement with some of the all-electron calculations. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:[Display omitted] • First microwave spectrum measurements for the butadiene ruthenium tricarbonyl complex. • Extensive high level calculations on the molecular structure and nuclear quadrupole coupling for this complex. • First resolved and analysed 101Ru and 99Ru quadrupole coupling spectra in a molecule. • Core potential (ECP) basis sets give better structures; all-electron basis sets give better quadrupole calculations. The microwave spectrum of η4-butadiene ruthenium tricarbonyl was measured in the 5–15 GHz frequency range using a Flygare-Balle type pulsed beam Fourier transform microwave (FTMW) spectrometer. The rotational constants for the 102Ru isotopologue were determined to have the following values: A = 932.20099(42), B = 858.03248(47) and C = 831.35161(37) MHz. The centrifugal distortion constant d J is 0.0862(29)kHz. 22 a-dipole and 4c-dipole transitions were measured. Extensive high-level G16 calculations were made using DFT and MP2 methods with various basis sets, some including core-potentials (ECP). The best structure was calculated with Gaussian 16 using B3LYP/def2-QZVPP, which includes a core potential (ECP). Extensive all-electron calculations were made based on the best ECP structure to predict 101Ru and 99Ru quadrupole coupling strengths. Quadrupole hyperfine structure splittings were measured for both 101Ru and 99Ru. The hyperfine structure splittings for the 101Ru nuclear quadrupole were measured, yielding the values of 1.5χ aa = 98.12(17) MHz and 0.25(χ bb -χ cc) = 36.059(30). Measured hyperfine structure splittings for 99Ru quadrupole coupling yielded the values of 1.5χ aa = 16.99(77) MHz and 0.25(χ bb -χ cc) = 6.23(32). These values are in reasonable agreement with some of the all-electron calculations. [ABSTRACT FROM AUTHOR]
ISSN:00222852
DOI:10.1016/j.jms.2024.111949