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Polymer Segments at the Folding Limit: Raman Scattering for the Diglyme Benchmark
Author(s) -
Bocklitz Sebastian,
Suhm Martin A.
Publication year - 2017
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.201701169
Subject(s) - diglyme , van der waals force , polar , polymer , chemical physics , chemistry , raman scattering , raman spectroscopy , london dispersion force , folding (dsp implementation) , molecular physics , physics , solvent , molecule , quantum mechanics , organic chemistry , electrical engineering , engineering
Methyl‐capped polyethers model flexible polar polymer chains. Their intrinsic all‐ trans conformational preference gives way to folded conformations if the chain is sufficiently long. We find by Raman cryospectroscopy in the gas phase and quantum chemical calculations that diglyme still prefers the stretched state, although folded variants come very close in energy. Three‐body dispersion correction or higher‐order electron correlation is important to match experiments, despite the polar character of C−O bonds. This turns oligoglymes into challenging benchmark systems for a balanced description of intra‐chain torsion and inter‐segment van der Waals attraction.