The characterization of the structures of molecular clusters, which serve as building blocks for bulk substances, provides crucial insight into the interactions between constituent units. Chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy, combined with state-of-the-art quantum chemical calculations, is a powerful tool for characterizing the structures of molecular clusters, as the rotational spectra are directly related to the mass distribution of a molecule or cluster. However, determining the structures of large or complex clusters from experimental rotational spectra remains challenging due to their structural flexibility. Ab initio and density functional theory calculations for searching their stable structures could be significantly time-consuming and method-dependent. To address these challenges, we have developed an approach that relies on the experimental rotational constants to search for potential molecular structures without quantum chemical optimization. Our approach involves creating an initial set of conformers through either a semi-empirical sampling program or the quasi-Monte Carlo method. After-ward, the trust region reflective algorithm is utilized for structure fitting. This procedure enables us to quickly generate potential conformers and gain access to precise structural information. We apply our fitting program to water hexamer and benzaldehyde-water clusters, and the resulting topological structures align extremely well with the experimental results.
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June 2023
Research Article|
June 01 2023
A fitting program for structural determination of molecular clusters from rotational spectroscopy†
Special Collection:
Virtual Issue on Molecular Spectroscopy (2023)
Xinlei Chen;
Xinlei Chen
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University
, Shanghai 200438, China
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Guanjun Wang;
Guanjun Wang
*
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University
, Shanghai 200438, China
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Weixing Li
Weixing Li
*
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University
, Shanghai 200438, China
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†
Part of the special topic for “the Chinese Chemical Society’s 17th National Chemical Dynamics Symposium”
Chin. J. Chem. Phys. 36, 298–306 (2023)
Article history
Received:
April 30 2023
Accepted:
May 25 2023
Citation
Xinlei Chen, Guanjun Wang, Weixing Li; A fitting program for structural determination of molecular clusters from rotational spectroscopy. Chin. J. Chem. Phys. 1 June 2023; 36 (3): 298–306. https://doi.org/10.1063/1674-0068/cjcp2304042
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