The adiabatic, relativistic, and quantum electrodynamics (QED) contributions to the pair potential of helium were computed, fitted separately, and applied, together with the nonrelativistic Born-Oppenheimer (BO) potential, in calculations of thermophysical properties of helium and of the properties of the helium dimer. An analysis of the convergence patterns of the calculations with increasing basis set sizes allowed us to estimate the uncertainties of the total interaction energy to be below 50 ppm for interatomic separations R smaller than 4 bohrs and for the distance R = 5.6 bohrs. For other separations, the relative uncertainties are up to an order of magnitude larger (and obviously still larger near R = 4.8 bohrs where the potential crosses zero) and are dominated by the uncertainties of the nonrelativistic BO component. These estimates also include the contributions from the neglected relativistic and QED terms proportional to the fourth and higher powers of the fine-structure constant α. To obtain such high accuracy, it was necessary to employ explicitly correlated Gaussian expansions containing up to 2400 terms for smaller R (all R in the case of a QED component) and optimized orbital bases up to the cardinal number X = 7 for larger R. Near-exact asymptotic constants were used to describe the large-R behavior of all components. The fitted potential, exhibiting the minimum of -10.996 ± 0.004 K at R = 5.608 0 ± 0.000 1 bohr, was used to determine properties of the very weakly bound (4)He(2) dimer and thermophysical properties of gaseous helium. It is shown that the Casimir-Polder retardation effect, increasing the dimer size by about 2 Å relative to the nonrelativistic BO value, is almost completely accounted for by the inclusion of the Breit-interaction and the Araki-Sucher contributions to the potential, of the order α(2) and α(3), respectively. The remaining retardation effect, of the order of α(4) and higher, is practically negligible for the bound state, but is important for the thermophysical properties of helium. Such properties computed from our potential have uncertainties that are generally significantly smaller (sometimes by nearly two orders of magnitude) than those of the most accurate measurements and can be used to establish new metrology standards based on properties of low-density helium.

We report a new determination of the Universal Gas Constant R: (8.314471 ±0.OOOOI4)J.mol-1 K-1• The uncertainty in the new value is 1.7 ppm (standard error), a factor of 5 smaller than the uncertainty in the best previous value. The gas constant was determined from measurements of the speed of sound in argon as a function of pressure at the temperature of the triple point of water. The speed of sound was measured with a spherical resonator whose volume was determined by weighing the mercury required to fill it at the temperature of the tri~le point. The molar mass of the argon was determined by comparing the speed of sound in it to the speed of sound in a standard sample of argon of accurately known chemical and isotoptic composition.

We review the principles, techniques and results from primary acoustic gas thermometry (AGT). Since the establishment of ITS-90, the International Temperature Scale of 1990, spherical and quasi-spherical cavity resonators have been used to realize primary AGT in the temperature range 7 K to 552 K. Throughout the sub-range 90 K < T < 384 K, at least two laboratories measured (T − T 90 ). (Here T is the thermodynamic temperature and T 90 is the temperature on ITS-90.) With a minor exception, the resulting values of (T − T 90 ) are mutually consistent within 3 × 10 −6 T . These consistent measurements were obtained using helium and argon as thermometric gases inside cavities that had radii ranging from 40 mm to 90 mm and that had walls made of copper or aluminium or stainless steel. The AGT values of (T − T 90 ) fall on a smooth curve that is outside ±u(T 90 ), the estimated uncertainty of T 90 . Thus, the AGT results imply that ITS-90 has errors that could be reduced in a future temperature scale. Recently developed techniques imply that low-uncertainty AGT can be realized at temperatures up to 1350 K or higher and also at temperatures in the liquid-helium range.

Gas-filled spherical resonators are excellent tools for routine measurement of thermophysical properties. The radially symmetric gas resonances are nondegenerate and have high Q’s (typically 2000–10 000). Thus they can be used with very simple instrumentation to measure the speed of sound in a gas with an accuracy of 0.02%. We have made a detailed study of a prototype resonator filled with argon (0.1–1.0 MPa) at 300 K, with the objective of discovering those phenomena which must be understood to use gas-filled spherical resonators to measure the thermodynamic temperature and the universal gas constant R. The resonance frequencies fN and half-widths gN were measured for nine radially symmetric modes and nine triply-degenerate nonradial modes with a precision near 10−7 fN. The data were used to develop and test theoretical models for this geometrically simple oscillating system. The basic model treats the following phenomena exactly for the case of a geometrically perfect sphere: (1) the thermal boundary layer near the resonator wall, (2) the viscous boundary layer (for nonradial modes), (3) bulk dissipation, and (4) the coupling of shell motion and gas motion. In addition, the following phenomena are included in the model through the use of perturbation theory: (5) ducts through the shell, (6) imperfect resonator geometry, and (7) the seam where the two hemispheres comprising the shell are joined. Some estimates of the effects of (8) roughness of the interior of the shell have also been made. Much of the lower pressure fN and gN data can be explained by our model of these phenomena to within ±5×10−6 fN when a single parameter c0/(V0)1/3 is fit to a single resonance frequency at a single pressure. In this parameter, c0 is the ideal-gas speed of sound and V0 is the resonator volume. If this volume were known, the prototype resonator could be used to measure the speed of sound of a gas with an accuracy approaching ±0.0005%. Improvements in resonator design which will circumvent difficulties discovered in this work are expected to lead to much better agreement between theory and the measured fN and gN.

Nonrelativistic clamped-nuclei energies of interaction between two ground-state hydrogen molecules with intramolecular distances fixed at their average value in the lowest rovibrational state have been computed. The calculations applied the supermolecular coupled-cluster method with single, double, and noniterative triple excitations [CCSD(T)] and very large orbital basis sets-up to augmented quintuple zeta size supplemented with bond functions. The same basis sets were used in symmetry-adapted perturbation theory calculations performed mainly for larger separations to provide an independent check of the supermolecular approach. The contributions beyond CCSD(T) were computed using the full configuration interaction method and basis sets up to augmented triple zeta plus midbond size. All the calculations were followed by extrapolations to complete basis set limits. For two representative points, calculations were also performed using basis sets with the cardinal number increased by one or two. For the same two points, we have also solved the Schrodinger equation directly using four-electron explicitly correlated Gaussian (ECG) functions. These additional calculations allowed us to estimate the uncertainty in the interaction energies used to fit the potential to be about 0.15 K or 0.3% at the minimum of the potential well. This accuracy is about an order of magnitude better than that achieved by earlier potentials for this system. For a near-minimum T-shaped configuration with the center-of-mass distance R=6.4 bohrs, the ECG calculations give the interaction energy of -56.91+/-0.06 K, whereas the orbital calculations in the basis set used for all the points give -56.96+/-0.16 K. The computed points were fitted by an analytic four-dimensional potential function. The uncertainties in the fit relative to the ab initio energies are almost always smaller than the estimated uncertainty in the latter energies. The global minimum of the fit is -57.12 K for the T-shaped configuration at R=6.34 bohrs. The fit was applied to compute the second virial coefficient using a path-integral Monte Carlo approach. The achieved agreement with experiment is substantially better than in any previous work.