Measurements of the microwave spectrum and calculations of the molecular structure for η4-butadiene osmium tricarbonyl

Adam M. Daly; Stephen G. Kukolich

doi:10.1016/j.jms.2025.112050

Measurements of the microwave spectrum and calculations of the molecular structure for η⁴-butadiene osmium tricarbonyl

Adam M. Daly
, Stephen G. Kukolich

Research output: Contribution to journal › Article › peer-review

Abstract

The microwave spectrum of η⁴-butadiene osmium tricarbonyl was measured in the 6–12 GHz frequency range using a Flygare-Balle type pulsed beam Fourier transform microwave (FTMW) spectrometer. The rotational constants for the ¹⁹²Os isotopologues were determined to have the following values: A = 939.4(2), B = 849.08(1) and C = 816.71(1) MHz. The centrifugal distortion constant is D_J = 0.60(7) kHz. 16 a-dipole transitions were measured and included in the fit. Extensive high-level G16 calculations were made using DFT methods with various basis sets, including core-potentials (ECP). The best structure was calculated with Gaussian 16 using B3LYP/def2-QZVPP, which includes a core potential (ECP). The best calculated values are in very good agreement with the experimental values.

Original language	English (US)
Article number	112050
Journal	Journal of Molecular Spectroscopy
Volume	413-414
DOIs	https://doi.org/10.1016/j.jms.2025.112050
State	Published - Dec 2025
Externally published	Yes

Keywords

Microwave spectroscopy
Molecular structure calculations
Molecular structure data
Transition metal complex

ASJC Scopus subject areas

Atomic and Molecular Physics, and Optics
Spectroscopy
Physical and Theoretical Chemistry

Access to Document

10.1016/j.jms.2025.112050

Cite this

@article{8d77ca5860144ca8aa517fc167efd3ec,

title = "Measurements of the microwave spectrum and calculations of the molecular structure for η4-butadiene osmium tricarbonyl",

abstract = "The microwave spectrum of η4-butadiene osmium tricarbonyl was measured in the 6–12 GHz frequency range using a Flygare-Balle type pulsed beam Fourier transform microwave (FTMW) spectrometer. The rotational constants for the 192Os isotopologues were determined to have the following values: A = 939.4(2), B = 849.08(1) and C = 816.71(1) MHz. The centrifugal distortion constant is DJ = 0.60(7) kHz. 16 a-dipole transitions were measured and included in the fit. Extensive high-level G16 calculations were made using DFT methods with various basis sets, including core-potentials (ECP). The best structure was calculated with Gaussian 16 using B3LYP/def2-QZVPP, which includes a core potential (ECP). The best calculated values are in very good agreement with the experimental values.",

keywords = "Microwave spectroscopy, Molecular structure calculations, Molecular structure data, Transition metal complex",

author = "Daly, \{Adam M.\} and Kukolich, \{Stephen G.\}",

note = "Publisher Copyright: {\textcopyright} 2025 Elsevier Inc.",

year = "2025",

month = dec,

doi = "10.1016/j.jms.2025.112050",

language = "English (US)",

volume = "413-414",

journal = "Journal of Molecular Spectroscopy",

issn = "0022-2852",

publisher = "Academic Press Inc.",

}

TY - JOUR

T1 - Measurements of the microwave spectrum and calculations of the molecular structure for η4-butadiene osmium tricarbonyl

AU - Daly, Adam M.

AU - Kukolich, Stephen G.

PY - 2025/12

Y1 - 2025/12

N2 - The microwave spectrum of η4-butadiene osmium tricarbonyl was measured in the 6–12 GHz frequency range using a Flygare-Balle type pulsed beam Fourier transform microwave (FTMW) spectrometer. The rotational constants for the 192Os isotopologues were determined to have the following values: A = 939.4(2), B = 849.08(1) and C = 816.71(1) MHz. The centrifugal distortion constant is DJ = 0.60(7) kHz. 16 a-dipole transitions were measured and included in the fit. Extensive high-level G16 calculations were made using DFT methods with various basis sets, including core-potentials (ECP). The best structure was calculated with Gaussian 16 using B3LYP/def2-QZVPP, which includes a core potential (ECP). The best calculated values are in very good agreement with the experimental values.

AB - The microwave spectrum of η4-butadiene osmium tricarbonyl was measured in the 6–12 GHz frequency range using a Flygare-Balle type pulsed beam Fourier transform microwave (FTMW) spectrometer. The rotational constants for the 192Os isotopologues were determined to have the following values: A = 939.4(2), B = 849.08(1) and C = 816.71(1) MHz. The centrifugal distortion constant is DJ = 0.60(7) kHz. 16 a-dipole transitions were measured and included in the fit. Extensive high-level G16 calculations were made using DFT methods with various basis sets, including core-potentials (ECP). The best structure was calculated with Gaussian 16 using B3LYP/def2-QZVPP, which includes a core potential (ECP). The best calculated values are in very good agreement with the experimental values.

KW - Microwave spectroscopy

KW - Molecular structure calculations

KW - Molecular structure data

KW - Transition metal complex

UR - https://www.scopus.com/pages/publications/105015406085

UR - https://www.scopus.com/pages/publications/105015406085#tab=citedBy

U2 - 10.1016/j.jms.2025.112050

DO - 10.1016/j.jms.2025.112050

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SN - 0022-2852

VL - 413-414

JO - Journal of Molecular Spectroscopy

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