Journal Article

PUBDB-2025-04476

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png CO$_2$ Versus CH$_4$ Aggregation on Trifluorobenzene: Molecular Level Characterization via Rotational Spectroscopy

Xie, F. (Corresponding author)DESY* ; Schnell, M.CFEL*DESY*

2025
Wiley-VCH Weinheim

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Please use a persistent id in citations: doi:10.1002/ange.202513517  doi:10.3204/PUBDB-2025-04476

Abstract: The cluster growth behavior of CO$_2$ and CH$_4$ on an aromatic ligand has been studied through the unambiguous identification of complex structures of 1,2,3-trifluorobenzene-(CO$_2$)1–4 and -ß(CH4)1–2 using broadband rotational spectroscopy in conjunction with extensive theoretical calculations. The results reveal a contrast in the thermodynamically favorable ligand-gas binding sites and noncovalent interactions of the two gaseous molecules on the ligand. The observation of a tunneling splitting and large centrifugal distortions indicates that CH$_4$ molecules bind to the fluorinated π system via three weak hydrogen bonds without CH$_4$ self-interactions, resulting in an effective structure displaced toward the dissociation limit. Conversely, CO$_2$ shows diverse and stronger intermolecular interactions with the fluorinated benzene, including F─C tetrel bonding, lone pair to π-hole interactions, $π–π$ stacking, and a significant contribution from CO$_2$ self-interactions. The thorough examination of ligand–gas interactions and aggregation patterns highlights the significant capacity and selectivity of the fluorinated aromatic ligand for accepting CO$_2$ over CH$_4$.

Note: The authors acknowledge financial support by the Deutsche Forschungsgemeinschaft in the context of the priority program SPP1807

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Contributing Institute(s):

1. Spectroscopy of molecular processes (FS-SMP)

Research Program(s):

1. 631 - Matter – Dynamics, Mechanisms and Control (POF4-631) (POF4-631)

Experiment(s):

1. No specific instrument

Appears in the scientific report 2025

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Database coverage:
; ; ; DEAL Wiley ; Ebsco Academic Search ; Nationallizenz ; SCOPUS

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