The Role of Non‑Covalent Interactions on Cluster Formation: Pentamer, Hexamers and Heptamer of Difluoromethane

ACS Citation

Calabrese, C.; Temelso, B.; Usabiaga, I.; Seifert, N.A.; Basterretxea, F.J.; Prampolini, G.; Shields, G.C.; Pate, B.H.; Evangelisti, L.; Cocinero, E.J. "The Role of Non-Covalent Interactions on Cluster Formation: Pentamer, Hexamers and Heptamer of Difluoromethane." Angew. Chem. Int. Ed., 2021, 60, 16894.

Abstract

The role of non-covalent interactions (NCIs) has broadened with the inclusion of new types of interactions and a plethora of weak donor/acceptor partners. This work illustrates the potential of chirped-pulse Fourier transform microwave technique, which has revolutionized the field of rotational spectroscopy. In particular, it has been exploited to reveal the role of NCIs’ in the molecular self-aggregation of difluoromethane where a pentamer, two hexamers and a heptamer were detected. The development of a new automated assignment program and a sophisticated computational screening protocol was essential for identifying the homoclusters in conditions of spectral congestion. The major role of dispersion forces leads to less directional interactions and more distorted structures than those found in polar clusters, although a detailed analysis demonstrates that the dominant interaction energy is the pairwise interaction. The tetramer cluster is identified as a structural unit in larger clusters, representing the maximum expression of bond between dimers.

Source Name

Angewandte Chemie International Edition

Publication Date

6-24-2021

Volume

60

Page(s)

16894-16899

Document Type

Citation

Citation Type

Article

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