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rdf:type
lifeskim:mentions
pubmed:issue
24
pubmed:dateCreated
2004-7-22
pubmed:abstractText
Dielectric relaxation times are often interpreted in terms of the reorientation of dipolar species or aggregates. The relevant time correlation function contains, however, cross terms between dipole moments of different particles. In the static case, these cross terms are accounted for by the Kirkwood factor g(K). Theories and molecular dynamics simulations suggest that such cross correlations may also affect the time-dependent properties, as reflected in the dielectric spectra. We present an experimental method for detecting effects of such cross correlations in dielectric spectra by a comparative analysis of dielectric and magnetic relaxation data. We demonstrate that such collective contributions can substantially affect dielectric relaxation. Experiments for n-pentanol (g(K)=3.06 at 298 K) and 2,2-dimethyl-3-ethyl-pentane-3-ol (g(K)=0.59) and their solutions in carbon tetrachloride show that in systems with g(K)>1, the cross correlations slow down dielectric relaxation. In systems with g(K)<1, dielectric relaxation is enhanced. The results conform to theoretical predictions by Madden and Kivelson [Adv. Chem. Phys. 56, 467 (1984)] and to results of molecular dynamics simulations. The relaxation enhancement by cross terms in the case of g(K)<1 is difficult to rationalize by conventional models of dielectric relaxation.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Jun
pubmed:issn
0021-9606
pubmed:author
pubmed:copyrightInfo
(c) 2004 American Institute of Physics.
pubmed:issnType
Print
pubmed:day
22
pubmed:volume
120
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
11692-7
pubmed:year
2004
pubmed:articleTitle
Collective contributions to the dielectric relaxation of hydrogen-bonded liquids.
pubmed:affiliation
Physikalische Chemie II, Ruhr-Universität, D-44780 Bochum, Germany.
pubmed:publicationType
Journal Article