Affiliation:
1. School of Molecular Sciences The University of Western Australia 35 Stirling Hwy Crawley Australia 6009
2. Department of Chemistry Physical and Theoretical Chemistry Laboratory University of Oxford South Parks Road Oxford United Kingdom OX1 3QZ
3. School of Science Edith Cowan University Joondalup Australia 6027
Abstract
AbstractGas‐phase solvation of halides by 1,3‐butadiene has been studied via a combination of photoelectron spectroscopy and density functional theory. Photoelectron spectra for X−⋯(C4H6)n (X=Cl, Br, I where n=1‐3, 1–3 and 1–7 respectively) are presented. For all complexes, the calculated structures indicate that butadiene is bound in a bidentate fashion through hydrogen‐bonding, with the chloride complex showing the greatest degree of stabilisation of the internal C−C rotation of cis‐butadiene. In both Cl− and Br− complexes, the first solvation shell is shown to be at least
from the vertical detachment energies (VDEs), however for I−, increases in the VDE may suggest a metastable, partially filled, first solvation shell for
and a complete shell at
. These results have implications for gas‐phase clustering in atmospheric and extraterrestrial environments.
Funder
Danmarks Grundforskningsfond
Australian Research Council
Subject
General Chemistry,Catalysis,Organic Chemistry