Insight into the halogen-bond nature of noble gas-chlorine systems by molecular beam scattering experiments
| Autor: | Francesco Tarantelli, Fernando Pirani, Stefano Falcinelli, Diego Cesario, Francesca Nunzi, David Cappelletti, Luiz F. Roncaratti, Leonardo Belpassi |
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| Přispěvatelé: | AIMMS, Theoretical Chemistry |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Materials science
Halogen bond Scattering Ab initio General Physics and Astronomy 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Potential energy Molecular physics 0104 chemical sciences symbols.namesake Ab initio quantum chemistry methods Excited state Atom symbols SDG 7 - Affordable and Clean Energy Physical and Theoretical Chemistry van der Waals force 0210 nano-technology |
| Zdroj: | Physical Chemistry Chemical Physics, 21(14), 7330-7340. The Royal Society of Chemistry Nunzi, F, Cesario, D, Belpassi, L, Tarantelli, F, Roncaratti, L F, Falcinelli, S, Cappelletti, D & Pirani, F 2019, ' Insight into the halogen-bond nature of noble gas-chlorine systems by molecular beam scattering experiments, Ab initio calculations and charge displacement analysis ', Physical Chemistry Chemical Physics, vol. 21, no. 14, pp. 7330-7340 . https://doi.org/10.1039/c9cp00300b |
| ISSN: | 1463-9076 |
| DOI: | 10.1039/c9cp00300b |
| Popis: | We have carried out molecular-beam scattering experiments and high-level ab initio investigations on the potential energy surfaces of a series of noble-gas-Cl 2 adducts. This effort has permitted the construction of a simple, reliable and easily generalizable analytical model potential formulation, which is based on a few physically meaningful parameters of the interacting partners and transparently shows the origin, strength, and stereospecificity of the various interaction components. The results demonstrate quantitatively beyond doubt that the interaction between a noble-gas (Ng) atom-even He-and Cl 2 in a collinear configuration is characterized by weak halogen bond (XB) formation, accompanied by charge transfer (CT) from the Ng to chlorine. This characteristic, which stabilizes the adduct, rapidly disappears on going towards the T-shaped configuration, dominated by pure van der Waals (vdW) forces. Similarly, a pure vdW interaction takes place-with no CT component in any configuration-if Cl 2 is present in the lowest π g ∗ → σ u ∗ excited state, because the change in electron density that accompanies the excitation eliminates the Cl 2 polar flattening and σ hole, making the XB interaction inaccessible. |
| Databáze: | OpenAIRE |
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