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Effects of pressure on the dielectric properties and phase transitions of the 2-D antiferroelectric squaric acid: (H/sub 2/C/sub 4/O/sub 4/ and D/sub 2/C/sub 4/O/sub 4/)

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:5939588

The pressure dependences of the dielectric properties and phase transitions of squaric acid, H/sub 2/C/sub 4/O/sub 4/, and its deuterated analog, D/sub 2/C/sub 4/O/sub 4/, were investigated. The transition temperatures at 1 bar are 375.5 +- 1.0 K and 527.5 +- 2.0 K, respectively, and decrease with pressure at initial rates of 105.6 +- 2.0 K/GPa and 102.5 +- 2.0K/GPa. It is argued that the large hydrogen isotope effect on T/sub c/ can be accounted for on the basis of the elongation of the O--HxxxO bond resulting from deuteration. This elongation causes a modification of the double-well potential along this bond. It is not necessary to invoke proton tunneling. The lack of an appreciable isotope effect on dT/sub c//dP supports the absence of tunneling. An interesting aspect of the results is the appearance of a dome-shaped feature in the real part of the dielectric constant just above T/sub c/ in both crystals. This feature, which is reminiscent of the behavior of the magnetic susceptibility of antiferromagnets above the Neel temperature, is discussed. The results on D/sub 2/C/sub 4/O/sub 4/ suggest the possible existence of a pressure-induced phase transition at approx.0.8 GPa. The dielectric loss of this crystal is large both below and above T/sub c/. This is attributed to the high conductivity of D/sub 2/C/sub 4/O/sub 4/ on approaching the melting (or dissociation) temperature. The activation energies for conduction and their pressure dependences both above and below T/sub c/ are determined and discussed.

Research Organization:
Sandia Laboratories, Albuquerque, New Mexico 87185
OSTI ID:
5939588
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 71:3; ISSN JCPSA
Country of Publication:
United States
Language:
English