title: Role of quantum fluctuations in structural dynamics of liquids of light molecules.
abstract: A possible role of quantum effects, such as tunneling and zero-point energy, in the structural dynamics of supercooled liquids is studied by dielectric spectroscopy. The presented results demonstrate that the liquids, bulk 3-methyl pentane and confined normal and deuterated water, have low glass transition temperature and unusually low for their class of materials steepness of the temperature dependence of structural relaxation (fragility). Although we do not find any signs of tunneling in the structural relaxation of these liquids, their unusually low fragility can be well described by the influence of the quantum fluctuations. Confined water presents an especially interesting case in comparison to the earlier data on bulk low-density amorphous and vapor deposited water. Confined water exhibits a much weaker isotope effect than bulk water, although the effect is still significant. We show that it can be ascribed to the change of the energy barrier for relaxation due to a decrease in the zero-point energy upon D/H substitution. The observed difference in the behavior of confined and bulk water demonstrates high sensitivity of quantum effects to the barrier heights and structure of water. Moreover, these results demonstrate that extrapolation of confined water properties to the bulk water behavior is questionable.
authors.affiliation: Department of Chemistry and Joint Institute for Neutron Sciences, University of Tennessee, Knoxville, Tennessee 37996, USA.
authors.forename: A
authors.initials: A
authors.lastname: Agapov
authors.affiliation: Department of Chemistry and Joint Institute for Neutron Sciences, University of Tennessee, Knoxville, Tennessee 37996, USA.
authors.forename: V N
authors.initials: VN
authors.lastname: Novikov
authors.affiliation: Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: A
authors.initials: A
authors.lastname: Kisliuk
authors.affiliation: School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287-1604, USA.
authors.forename: R
authors.initials: R
authors.lastname: Richert
authors.affiliation: Department of Chemistry and Joint Institute for Neutron Sciences, University of Tennessee, Knoxville, Tennessee 37996, USA.
authors.forename: A P
authors.initials: AP
authors.lastname: Sokolov