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Unveiling the Sulfur–Sulfur Bridge: Accurate Structural and Energetic Characterization of a Homochalcogen Intermolecular Bond
- Publication Year :
- 2018
-
Abstract
- open 12 si MIUR “PRIN 2015” funds (Grant Number 2015F59J3R) By combining rotational spectroscopy in supersonic expansion with the capability of state-of-the-art quantum-chemical computations in accurately determining structural and energetic properties, the genuine nature of a sulfur–sulfur chalcogen bond between dimethyl sulfide and sulfur dioxide has been unveiled in a gas-jet environment free from collision, solvent and matrix perturbations. A SAPT analysis pointed out that electrostatic S⋅⋅⋅S interactions play the dominant role in determining the stability of the complex, largely overcoming dispersion and C−H⋅⋅⋅O hydrogen-bond contributions. Indeed, in agreement with the analysis of the quadrupole-coupling constants and of the methyl internal rotation barrier, the NBO and NOCV/CD approaches show a marked charge transfer between the sulfur atoms. Based on the assignment of the rotational spectra for 7 isotopologues, an accurate semi-experimental equilibrium structure for the heavy-atom backbone of the molecular complex has been determined, which is characterized by a S⋅⋅⋅S distance (2.947(3) Å) well below the sum of van der Waals radii. embargoed_20191010 Obenchain, Daniel A.; Spada, Lorenzo; Alessandrini, Silvia; Rampino, Sergio; Herbers, Sven; Tasinato, Nicola; Mendolicchio, Marco; Kraus, Peter; Gauss, Jürgen; Puzzarini, Cristina; Grabow, Jens-Uwe*; Barone, Vincenzo Obenchain, Daniel A.; Spada, Lorenzo; Alessandrini, Silvia; Rampino, Sergio; Herbers, Sven; Tasinato, Nicola; Mendolicchio, Marco; Kraus, Peter; Gauss, Jürgen; Puzzarini, Cristina; Grabow, Jens-Uwe*; Barone, Vincenzo
- Subjects :
- Materials science
chemistry.chemical_element
02 engineering and technology
bond analysi
010402 general chemistry
01 natural sciences
Quantum chemistry
Catalysis
Catalysi
bond analysis
quantum chemistry
symbols.namesake
Chalcogen
rotational spectroscopy
Van der Waals radius
Physics::Chemical Physics
Astrophysics::Galaxy Astrophysics
energy and charge decomposition models
semi-experimental equilibrium structure
Chemistry (all)
energy and charge decomposition model
010405 organic chemistry
Intermolecular force
General Medicine
General Chemistry
021001 nanoscience & nanotechnology
Sulfur
0104 chemical sciences
chemistry
Chemical physics
symbols
Rotational spectroscopy
0210 nano-technology
Dispersion (chemistry)
Natural bond orbital
Subjects
Details
- Language :
- English
- Database :
- OpenAIRE
- Accession number :
- edsair.doi.dedup.....4a9bd3a63dadc0e53decb11061e342d4