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Measurement of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mo>(</mml:mo><mml:mfrac><mml:mrow><mml:mi>∂</mml:mi><mml:mi>P</mml:mi></mml:mrow><mml:mrow><mml:mi>∂</mml:mi><mml:mi>T</mml:mi></mml:mrow></mml:mfrac><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mi>V</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math>and Related Properties in Solidified Gases. II. Solid<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">H</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>

J.F. JarvisDepartment of Physics, Duke University, Durham, North CarolinaHORST MEYERDepartment of Physics, Duke University, Durham, North CarolinaDietolf RammDepartment of Physics, Duke University, Durham, North Carolina
1969lv
ABI

Abstract

We report measurements and their analysis of pressure changes with temperature and ortho-${\mathrm{H}}_{2}$ concentration in solid ${\mathrm{H}}_{2}$ in both the hcp and cubic phases. The temperature range extended from 0.4 to 4.2\ifmmode^\circ\else\textdegree\fi{}K, and the concentration $c$ of ortho-${\mathrm{H}}_{2}$ was between 0.005 and 0.94. The measurements were carried out by means of a sensitive capacitance strain gauge capable of resolving pressure changes of 2\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}5}$ bar. The categories of experiments performed were (1) determination of the pressure $P$ in the hcp phase as a function of ortho concentration at several temperatures; (2) determination of the pressure difference $P (\mathrm{hcp})\ensuremath{-}P (\mathrm{cubic})$ as a function of ortho concentration, and study of the hysteresis in both pressure and temperature of the hcp-to-cubic transition; and (3) measurement of ${(\frac{\ensuremath{\partial}P}{\ensuremath{\partial}T})}_{V}$ at constant ortho concentration in the hcp phase at several different ortho concentrations. The results were analyzed in terms of a lattice contribution and an electric quadrupole-quadrupole (EQQ) interaction, neglecting any effects from other interactions and from crystalline fields. The EQQ interaction parameter determined experimentally was $\ensuremath{\Gamma}=\frac{6{e}^{2}{Q}^{2}}{25{R}^{5}}$, where $\mathrm{eQ}$ is the quadrupole moment of the orthomolecule in the state $J=1$, and $R$ is the nearest-neighbor distance. The theoretical value for a rigid lattice is $\frac{\ensuremath{\Gamma}}{{k}_{B}}=1.00$\ifmmode^\circ\else\textdegree\fi{}K. The results from (1) and (2), extrapolated to pure ortho-${\mathrm{H}}_{2}$, were analyzed using the theory of Miyagi and Nakamura and gave $\frac{\ensuremath{\Gamma}}{{k}_{B}}=0.82\ifmmode\pm\else\textpm\fi{}0.04$\ifmmode^\circ\else\textdegree\fi{}K (value extrapolated to $P=0$). This value was confirmed from the temperature of the maximum of ${(\frac{\ensuremath{\partial}P}{\ensuremath{\partial}T})}_{V}$ at low ortho concentrations. The discrepancy between the experimental and the theoretical values of $\ensuremath{\Gamma}$ is briefly discussed. From ${(\frac{\ensuremath{\partial}P}{\ensuremath{\partial}T})}_{V}$ data with almost pure para-${\mathrm{H}}_{2}$ and from comparison with specific-heat data due to Ahlers, a lattice Gr\"uneisen constant ${\ensuremath{\gamma}}_{L}=2.06\ifmmode\pm\else\textpm\fi{}0.1$ was found. The Gr\"uneisen constant of the EQQ interaction was found to be ${\ensuremath{\gamma}}_{\mathrm{EQQ}}=1.62\ifmmode\pm\else\textpm\fi{}0.1$, in agreement with the theoretically expected value. Evidence was found for redistribution of orthomolecules at low ortho concentration as a function of time. The theoretical expectations for a thermodynamic-equilibrium distribution of molecules in the lattice and that for a random high-temperature distribution are compared with experimental results.

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