Modifying hydrogen-bonded structures by physical vapor deposition: 4-methyl-3-heptanol

A. R. Young-Gonzales, A. Guiseppi-Elie, M. D. Ediger, Ranko Richert

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

We prepared films of 4-methyl-3-heptanol by vapor depositing onto substrates held at temperatures between Tdep = 0.6Tg and Tg, where Tg is the glass transition temperature. Using deposition rates between 0.9 and 6.0 nm/s, we prepared films about 5 μm thick and measured the dielectric properties via an interdigitated electrode cell onto which films were deposited. Samples prepared at Tdep = Tg display the dielectric behavior of the ordinary supercooled liquid. Films deposited at lower deposition temperatures show a high dielectric loss upon heating toward Tg, which decreases by a factor of about 12 by annealing at Tg = 162 K. This change is consistent with either a drop of the Kirkwood correlation factor, gk, by a factor of about 10, or an increase in the dielectric relaxation times, both being indicative of changes toward ring-like hydrogen-bonded structure characteristic of the ordinary liquid. We rationalize the high dielectric relaxation amplitude in the vapor deposited glass by suggesting that depositions at low temperature provide insufficient time for molecules to form ring-like supramolecular structures for which dipole moments cancel. Surprisingly, above Tg of the ordinary liquid, these vapor deposited films fail to completely recover the dielectric properties of the liquid obtained by supercooling. Instead, the dielectric relaxation remains slower and its amplitude much higher than that of the equilibrium liquid state, indicative of a structure that differs from the equilibrium liquid up to at least Tg + 40 K.

Original languageEnglish (US)
Article number194504
JournalJournal of Chemical Physics
Volume147
Issue number19
DOIs
StatePublished - Nov 21 2017

Fingerprint

Heptanol
Physical vapor deposition
Hydrogen
vapor deposition
Dielectric relaxation
Liquids
hydrogen
liquids
Vapors
vapors
Dielectric properties
dielectric properties
Supercooling
rings
Dipole moment
supercooling
Dielectric losses
Deposition rates
dielectric loss
Relaxation time

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Modifying hydrogen-bonded structures by physical vapor deposition : 4-methyl-3-heptanol. / Young-Gonzales, A. R.; Guiseppi-Elie, A.; Ediger, M. D.; Richert, Ranko.

In: Journal of Chemical Physics, Vol. 147, No. 19, 194504, 21.11.2017.

Research output: Contribution to journalArticle

Young-Gonzales, A. R. ; Guiseppi-Elie, A. ; Ediger, M. D. ; Richert, Ranko. / Modifying hydrogen-bonded structures by physical vapor deposition : 4-methyl-3-heptanol. In: Journal of Chemical Physics. 2017 ; Vol. 147, No. 19.
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