Structure of Furan from 44 Isotopologues─Resolving Differences in the Theoretical (re) and Semi-Experimental Equilibrium (reSE) Structures.
5 affiliations
- 1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin53706, United States.
- 2Quantum Theory Project, Departments of Physics and Chemistry, University of Florida, Gainesville, Florida32611, United States.
- 3Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts02139, United States.
- 4Center for Astrophysics | Harvard & Smithsonian, 60 Garden Street, Cambridge, Massachusetts02138, United States.
- 5National Radio Astronomy Observatory, 520 Edgemont Road, Charlottesville, Virginia22903, United States.
Abstract
The rotational spectra of furan and numerous isotopologues were recorded and analyzed between 6 and 750 GHz. High-temperature, high-pressure, base-catalyzed H/D exchange was employed to create a mixture of all possible furan-dx isotopologues, allowing for the measurement and analysis of the rotational spectra of 44 furan isotopologues. The experimental rotational constants of these isotopologues, combined with CCSD(T)/cc-pCVTZ corrections for the effects of vibration-rotation interaction and the electron-mass distribution, were used to determine a semi-experimental equilibrium (reSE) structure of furan. The large number of isotopologues used, including 35 isotopologues observed for the first time, allowed for the determination of the reSE structure to a high level of accuracy and precision (≤0.0003 Å uncertainties in bond distances and ≤0.02° in bond angles). The current study additionally corrects for differences in principal axis rotation between the structure at which the vibration-rotation interaction constants were evaluated (CCSD(T)/cc-pCVTZ) and the reSE structure. The difference in rotation between these two structures had been previously reported, but not addressed. The "best theoretical estimate" (BTE) for the structure of furan was determined using a CCSD(T)/cc-pCV5Z geometry, with additional corrections addressing finite basis set, higher-level electron correlation, and relativistic effects, as well as the diagonal Born-Oppenheimer correction. The BTE structure of furan is compared to the reSE structure of furan, which is also compared to the previously determined reSE structure of its sulfur-containing analogue, thiophene.
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BibTeX
@article{mehalko2026structure,
title = {{Structure of Furan from 44 Isotopologues─Resolving Differences in the Theoretical (re) and Semi-Experimental Equilibrium (reSE) Structures.}},
author = {Kolton T Mehalko and Brian J Esselman and Peter R Franke and Martin S Holdren and Gabi Wenzel and D Archie Stewart and Zachary P Burke and Brett A McGuire and R Claude Woods and Robert J McMahon},
journal = {The journal of physical chemistry. A},
year = {2026},
month = oct,
doi = {10.1021/acs.jpca.6c04036},
url = {https://europepmc.org/article/MED/42917957},
note = {CC BY},
}
RIS
TY - JOUR
TI - Structure of Furan from 44 Isotopologues─Resolving Differences in the Theoretical (re) and Semi-Experimental Equilibrium (reSE) Structures.
AU - Kolton T Mehalko
AU - Brian J Esselman
AU - Peter R Franke
AU - Martin S Holdren
AU - Gabi Wenzel
AU - D Archie Stewart
AU - Zachary P Burke
AU - Brett A McGuire
AU - R Claude Woods
AU - Robert J McMahon
PY - 2026
DA - 2026/10/01
JO - The journal of physical chemistry. A
DO - 10.1021/acs.jpca.6c04036
UR - https://europepmc.org/article/MED/42917957
AB - The rotational spectra of furan and numerous isotopologues were recorded and analyzed between 6 and 750 GHz. High-temperature, high-pressure, base-catalyzed H/D exchange was employed to create a mixture of all possible furan-dx isotopologues, allowing for the measurement and analysis of the rotational spectra of 44 furan isotopologues. The experimental rotational constants of these isotopologues, combined with CCSD(T)/cc-pCVTZ corrections for the effects of vibration-rotation interaction and the electron-mass distribution, were used to determine a semi-experimental equilibrium (reSE) structure of furan. The large number of isotopologues used, including 35 isotopologues observed for the first time, allowed for the determination of the reSE structure to a high level of accuracy and precision (≤0.0003 Å uncertainties in bond distances and ≤0.02° in bond angles). The current study additionally corrects for differences in principal axis rotation between the structure at which the vibration-rotation interaction constants were evaluated (CCSD(T)/cc-pCVTZ) and the reSE structure. The difference in rotation between these two structures had been previously reported, but not addressed. The "best theoretical estimate" (BTE) for the structure of furan was determined using a CCSD(T)/cc-pCV5Z geometry, with additional corrections addressing finite basis set, higher-level electron correlation, and relativistic effects, as well as the diagonal Born-Oppenheimer correction. The BTE structure of furan is compared to the reSE structure of furan, which is also compared to the previously determined reSE structure of its sulfur-containing analogue, thiophene.
SN - 1089-5639
SN - 1520-5215
ER -