The σ‐Hole Interaction Between Sulfur Hexafluoride and Ammonia Characterised by Broadband Rotational Spectroscopy
Author(s) -
Bittner Dror M.,
Zaleski Daniel P.,
Stephens Susanna L.,
Walker Nicholas R.,
Legon Anthony C.
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500455
Subject(s) - isotopologue , chemistry , rotational spectroscopy , spectroscopy , ab initio quantum chemistry methods , spectral line , ab initio , sulfur hexafluoride , atomic physics , molecular physics , molecule , physics , organic chemistry , quantum mechanics , astronomy
Abstract A weakly‐bound complex of SF 6 and NH 3 is generated within an expanding gas jet and characterised by broadband rotational spectroscopy. The spectra of isotopologues 32 SF 6 ⋅⋅⋅ 14 NH 3 , 32 SF 6 ⋅⋅⋅ 14 ND 3 , 32 SF 6 ⋅⋅⋅ 15 NH 3 and 34 SF 6 ⋅⋅⋅ 15 NH 3 are observed and assigned to determine the spectroscopic parameters. These parameters are consistent with the complex having a C 3 v symmetric rotor geometry, in which the nitrogen atom of NH 3 coordinates to SF 6 such that the C 3 v axis of the NH 3 sub‐unit is aligned with a local C 3 axis on the SF 6 sub‐unit. The geometry of the complex is rationalized in terms of a σ‐hole interaction. The observed spectra and ab initio calculations also reveal evidence of internal dynamics involving internal rotation of one monomer sub‐unit with respect to the other about the symmetry axis of the complex.