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Crystal surfaces play a pivotal role in governing various significant processes, such as adsorption, nucleation, wetting, friction, and wear. A fundamental property that influences these processes is the surface free energy, γ. We have directly calculated γ(T) for low-index faces of Lennard-Jones (LJ), germanium, and silicon crystals along their sublimation lines using the computational cleavage technique. Our calculations agree well with experimental values for Si(111) and Ge(111), highlighting the accuracy of the method and models used. For LJ crystals, we identified a premelting onset at Tpm = 0.75Tm, marked by a sharp increase in atom mobility within the second outermost surface layer. Notably, Tpm closely aligned with the endpoint of the LJ melting line at negative pressures, Tend = 0.76Tm. We hypothesize that the emergence and coexistence of a liquid film atop the LJ crystal at Tpm < T < Tm correspond to the metastable melting line under negative pressures experienced by stretched crystal surfaces. Furthermore, our study of thin LJ crystal slabs reveals that premelting-induced failure leads to recrystallization below the homogeneous freezing limit, offering a promising avenue to explore crystal nucleation and growth at extremely deep supercoolings. Finally, no evidence of premelting was detected in the model crystals of Ge and Si, which is consistent with the experimental observations. Overall, our findings offer valuable insights into crystal surface phenomena at the atomic scale. [ABSTRACT FROM AUTHOR]

Solid–fluid phase equilibria are difficult to predict in simulations because bound degrees of freedom in the crystal phase must be converted to free translations and rotations in the fluid phase. Here, we avoid the solid-to-fluid transformation step by starting with chemical potentials for two reference systems, one for the fluid phase and one for the solid phase. For the solid, we start from the Einstein crystal and transform to the fully interacting molecular crystal. For the fluid phase, we introduce a new reference system, the "centroid," and then transform to gas phase molecules. We illustrate the new calculations by predicting the sublimation vapor pressure of succinic acid in the temperature range of 300 K–350 K. [ABSTRACT FROM AUTHOR]

We have established an apparatus for terahertz and mid-infrared spectroscopy in an ultrahigh vacuum and have measured absorption spectra of D2O clusters trapped in solid Ar. To assign terahertz absorption peaks due to the D2O dimer, trimer, and tetramer, the dependence of the spectrum on the annealing temperature and D2O dilution was analyzed. The assignment was also examined by ab initio calculations with the use of the "our own N-layered integrated molecular orbital and molecular mechanics" method, where the flexibility of surrounding Ar atoms was systematically incorporated. We identified all the intermolecular fundamentals of the dimer and those with significant intensities of the trimer and tetramer, whose structural symmetries were revealed to be broken down. After isolating the D2O clusters in solid Ar, we sublimated only Ar atoms to leave behind matrix-sublimation ice, which was found to be amorphous- or crystal-like depending on the formation conditions: the dilution and sublimation temperature. The crystallinity of matrix-sublimation ice was determined by decomposing its terahertz spectrum into the spectra of amorphous and crystalline ices. Since the crystallinity got higher by raising the dilution and sublimation temperature, the diffusion of the D2O monomer on the surface of sublimating solid Ar was found to be crucial to the crystallization of the sublimation ice. [ABSTRACT FROM AUTHOR]

A comparative study of the lattice energy calculations for a data set of 25 molecular crystals is performed using an additive scheme based on the individual energies of up to four-body interactions calculated using the coupled clusters with iterative treatment of single and double excitations and perturbative triples correction (CCSD(T)) with an estimated complete basis set (CBS) description. The CCSD(T)/CBS values on lattice energies are used to estimate sublimation enthalpies which are compared with critically assessed and thermodynamically consistent experimental values. The average absolute percentage deviation of calculated sublimation enthalpies from experimental values amounts to 13% (corresponding to 4.8 kJ mol-1 on absolute scale) with unbiased distribution of positive to negative deviations. As pair interaction energies present a dominant contribution to the lattice energy and CCSD(T)/CBS calculations still remain computationally costly, benchmark calculations of pair interaction energies defined by crystal parameters involving 17 levels of theory, including recently developed methods with local and explicit treatment of electronic correlation, such as LCC and LCC-F12, are also presented. Locally and explicitly correlated methods are found to be computationally effective and reliable methods enabling the application of fragment-based methods for larger systems. [ABSTRACT FROM AUTHOR]

The claim that classical nucleation theory (CNT) correctly predicts the dependence on supersaturation of the steady-state rate of homogeneous nucleation is reexamined in light of recent experimental studies of nucleation of a range of substances, including water, argon, nitrogen, and several 1-alcohols. Based on these studies (which include, for water, a compilation of nine different studies), it is concluded that the dependence of nucleation rate on supersaturation is not correctly predicted by CNT. It is shown that CNT's incorrect prediction of the supersaturation dependence of nucleation rate is due to its incorrect prediction of the Gibbs free energy change associated with formation of small clusters from the monomer vapor, evaluated at the substance's equilibrium vapor pressure, even though that free energy change is itself a function only of temperature. [ABSTRACT FROM AUTHOR]

The non-covalent interactions in organic molecules are known to drive their self-assembly to form molecular crystals. We compare, in the case of anthracene and against experimental (electronic-only) sublimation energy, how modern quantum-chemical methods are able to calculate this cohesive energy taking into account all the interactions between occurring dimers in both first-and second-shells. These include both O(N6)- and O(N5)-scaling methods, Local Pair Natural Orbital-parameterized Coupled-Cluster Single and Double, and Spin-Component-Scaled-Mo\ller-Plesset perturbation theory at second-order, respectively, as well as the most modern family of conceived density functionals: double-hybrid expressions in several variants (B2-PLYP, mPW2-PLYP, PWPB95) with customized dispersion corrections (-D3 and -NL). All-in-all, it is shown that these methods behave very accurately producing errors in the 1-2 kJ/mol range with respect to the experimental value taken into account the experimental uncertainty. These methods are thus confirmed as excellent tools for studying all kinds of interactions in chemical systems. [ABSTRACT FROM AUTHOR]

Thin films of water under nanoscopic confinement are prevalent in natural and manufactured materials. To investigate the equilibrium and dynamic behavior of water in such environments, we perform molecular dynamics simulations of water confined between atomistically detailed hydrophobic plates at T = 298 K for pressures (-0.1) <= P <= 1.0 GPa and plate separations of 0.40 <= d <= 0.80 nm. From these simulations, we construct an expanded P-d phase diagram for confined water, and identify and characterize a previously unreported confined monolayer ice morphology. We also study the decompression-induced sublimation of bilayer ice in a d = 0.6 nm slit, employing principal component analysis to synthesize low-dimensional embeddings of the drying trajectories and develop insight into the sublimation mechanism. Drying is observed to proceed by the nucleation of a bridging vapor cavity at one corner of the crystalline slab, followed by expansion of the cavity along two edges of the plates, and the subsequent recession of the remaining promontory of bilayer crystal into the bulk fluid. Our findings have implications for the understanding of diverse phenomena in materials science, nanofluidics, and protein folding and aggregation. [ABSTRACT FROM AUTHOR]

A benchmark for non-covalent interactions in solids (C21) based on the experimental sublimation enthalpies and geometries of 21 molecular crystals is presented. Thermal and zero-point effects are carefully accounted for and reference lattice energies and thermal pressures are provided, which allow dispersion-corrected density functionals to be assessed in a straightforward way. Other thermal corrections to the sublimation enthalpy (the 2RT term) are reexamined. We compare the recently implemented exchange-hole dipole moment (XDM) model with other approaches in the literature to find that XDM roughly doubles the accuracy of DFT-D2 and non-local functionals in computed lattice energies (4.8 kJ/mol mean absolute error) while, at the same time, predicting cell geometries within less than 2% of the experimental result on average. The XDM model of dispersion interactions is confirmed as a very promising approach in solid-state applications. [ABSTRACT FROM AUTHOR]

We have studied, via laser absorption spectroscopy, the velocity distribution of 7Li atoms released from cryogenic matrices of solid neon or molecular hydrogen. The Li atoms are implanted into the Ne or H2 matrices - grown onto a sapphire substrate - by laser ablation of a solid Li or LiH precursor. A heat pulse is then applied to the sapphire substrate sublimating the matrix together with the isolated atoms. With a NiCr film resistor deposited directly onto the sapphire substrate we are able to transfer high instantaneous power to the matrix, thus reaching a fast sublimation regime. In this regime the Li atoms can get entrained in the released matrix gas, and we were also able to achieve matrix sublimation times down to 10 μs for both H2 or Ne matrix, enabling us to proceed with the trapping of the species of our interest such as atomic hydrogen, lithium, and molecules. The sublimation of the H2 matrix, with its large center-of-mass velocity, provides evidence for a new regime of one-dimensional thermalization. The laser ablated Li seems to penetrate the H2 matrix deeper than it does in Ne. [ABSTRACT FROM AUTHOR]

Fully relativistic, four-component density functional theory electronic structure calculations were performed for MBr5, MOBr3, MBr6-, KMBr6, and MBr5Cl- of group-5 elements Nb, Ta, and element 105, Db, with the aim to predict adsorption behaviour of the bromides in gas-phase chromatography experiments. It was shown that in the atmosphere of HBr/BBr3, the pentabromides are rather stable, and their stability should increase in the row Nb < Db < Ta. Several mechanisms of adsorption were considered. In the case of adsorption by van der Waals forces, the sequence in volatility of the pentabromides should be Nb < Ta < Db, being in agreement with the sublimation enthalpies of the Nb and Ta pentabromides. In the case of adsorption by chemical forces (on a quartz surface modified with KBr/KCl), formation of the MBr5L- (L = Cl, Br) complex should occur, so that the volatility should change in an opposite way, i.e., Nb > Ta > Db. This sequence is in agreement with the one observed in the 'one-atom-at-a-time' chromatography experiments. Some other scenarios, such as surface oxide formation were also considered but found to be irrelevant. [ABSTRACT FROM AUTHOR]

We have studied, via laser absorption spectroscopy, the velocity distribution of 7Li atoms released from a solid neon matrix at cryogenic temperatures. The Li atoms are implanted into the Ne matrix by laser ablation of a solid Li precursor. A heat pulse is then applied to the sapphire substrate sublimating the matrix together with the isolated atoms at around 12 K. We find interesting differences in the velocity distribution of the released Li atoms from the model developed for our previous experiment with Cr [R. Lambo, C. C. Rodegheri, D. M. Silveira, and C. L. Cesar, Phys. Rev. A 76, 061401(R) (2007)]. This may be due to the sublimation regime, which is at much lower flux for the Li experiment than for the Cr experiment, as well as to the different collisional cross sections between those species to the Ne gas. We find a drift velocity compatible with Li being thermally sublimated at 11-13 K, while the velocity dispersion around this drift velocity is low, around 5-7 K. With a slow sublimation of the matrix we can determine the penetration depth of the laser ablated Li atoms into the Ne matrix, an important information that is not usually available in most matrix isolation spectroscopy setups. The present results with Li, together with the previous results with Cr suggest this to be a general technique for obtaining cryogenic atoms, for spectroscopic studies, as well as for trap loading. The release of the isolated atoms is also a useful tool to study and confirm details of the matrix isolated atoms which are masked or poorly understood in the solid. [ABSTRACT FROM AUTHOR]

Homogeneous nucleation rates of the n-alkanes (CiH2i+2; i=7–10) were determined by combining information from pressure trace measurements and small angle x-ray scattering (SAXS) experiments in a supersonic Laval nozzle. The condensible vapor pressure pJ max, the temperature TJ max, the characteristic time ΔtJ max, and supersaturation SJ max corresponding to the peak nucleation rate Jmax were determined during the pressure trace measurements. These measurements also served as the basis for the subsequent SAXS experiments. Fitting the radially averaged SAXS spectrum yielded the mean droplet radius , 5≤/nm≤31, the width of the aerosol size distribution σ, 2≤σ/nm≤6, and the particle number density N, 7×1010

31P NMR spectroscopy has been used to elucidate the role of glass-forming sugars in the preservation of dipalmitoylphosphatidylcholine (DPPC) lipid bilayers. 31P wideline NMR spectra of freeze-dried pure DPPC, DPPC/trehalose, DPPC/glucose, and DPPC/hydroxyethyl starch (HES) mixtures collected in the temperature range of 25–80 °C have been simulated to obtain quantitative information about rotational dynamics and orientation of the lipid head groups in these media. In the case of pure DPPC, DPPC/glucose, and DPPC/HES, the gel-to-liquid crystalline phase transition of DPPC bilayer is characterized by a sudden increase in the rate of rotational diffusion of the PO4 head groups near 40 °C. The corresponding rotational jump frequency increases from a few kilohertz in the gel phase to at least several megahertz in the liquid crystalline phase. On the other hand, in the case of DPPC/trehalose mixture the temperature of this onset of rapid head group dynamics is increased by ∼10 °C. Trehalose reduces the lipid head group motions most effectively in the temperature range of T≤50 °C relevant for biopreservation. Additionally, and possibly more importantly, trehalose is found to strongly restrict any change in the orientation of the diffusion axis of the PO4 head groups during the phase transformation. This unique ability of trehalose to maintain the dynamical and orientational rigidity of lipid head groups is likely to be responsible for its superior ability in biopreservation. [ABSTRACT FROM AUTHOR]

Single and multiwalled nitrogen-doped carbon nanotubes were grown by chemical vapor deposition varying the feedstock composition between pure acetonitrile and ethanol/acetonitrile mixtures. The advantage of using C/N sources that develop close vapor pressure values has been used in order to elucidate the effects of the reaction atmosphere in the synthesis of N-doped nanotubes. Our findings show that the morphology of the nanotube material depends strongly on the composition of the reaction atmosphere. When carrying out the experiments in an atmosphere solely determined by the vapor pressure of the feedstock components, improved homogeneity is achieved with pure C/N sources or low concentration of the foreign solute. Under these conditions the temperature has strong influence in the diameter distribution. [ABSTRACT FROM AUTHOR]

Homogeneous nucleation of argon droplets has been measured with a newly designed cryogenic nucleation pulse chamber presented already in a previous paper [Fladerer and Strey, J. Chem. Phys. 124, 16 (2006)]. Here we present the first systematic nucleation onset data for argon measured in a temperature range from 42 to 58 K and for vapor pressures from 0.3 to 10 kPa. For these data we provide an analytical fit function. From the geometry of the optical detection system and the time of nucleation the experimental nucleation-rate range can be estimated. This allows a comparison of the data with the predictions of classical nucleation theory. We found 16–26 orders of magnitude difference between theory and experiment, and a too strong theoretical dependence of the nucleation rate on temperature. A comparison with the self-consistent theory of Girshick and Chiu [J. Chem. Phys. 93, 1273 (1990)] showed improved temperature dependence but still discrepancies of 11–17 orders of magnitude compared to experimental data. The thermodynamically consistent theory of Kashchiev [J. Chem. Phys. 118, 1837 (2003)] was found to agree rather well with experiment in respect to the temperature dependence and to predict rates about 5-7 orders of magnitude below the experimental ones. With the help of the Gibbs-Thomson equation we were able to evaluate the size of the critical nucleus to be 40–80 argon atoms. [ABSTRACT FROM AUTHOR]

The authors present new measurements of thermal and electrical properties for two porphyrin derivatives. They determine their sublimation enthalpy from the temperature dependence of the effusive beam intensity. The authors study H2TPP and Fe(TPP)Cl in matter-wave interferometry. Both molecules have nearly equal de Broglie wavelengths but different internal characteristics: only Fe(TPP)Cl exhibits an electric dipole moment of about 2.7 D and the authors discuss its influence on the molecular interference pattern. The authors add an external electric force field to the interferometer and use it to measure the scalar polarizability. They compare their experimental values α(H2TPP)=105±4±6 Å3 and α(Fe(TPP)Cl)=102±9±6 Å3 to ab initio calculations and they discuss the influence of thermal excitations on the polarizability. [ABSTRACT FROM AUTHOR]

Using molecular dynamics simulations, The authors studied the solid-vapor coexistence states of Lennard-Jones methane confined in slit-shaped graphite nanopores. Both the intrapore solid and extrapore vapor were simulated using a unit cell which they previously developed. Frozen critical condensates in the pores were cooled stepwise, and the equilibrium vapor pressure was determined at each temperature. The obtained solid-vapor coexistence curves were remarkably lower than that of the bulk phase. Their thermodynamic model successfully predicts the simulation results without the need to introduce any adjustable parameter, and thus proves its reliability. [ABSTRACT FROM AUTHOR]

The authors performed Gibbs ensemble simulations on the vapor-liquid equilibrium of water to investigate the influence of incorporating intramolecular degrees of freedom in the simple point charge (SPC) water model. Results for vapor pressures, saturation densities, heats of vaporization, and the critical point for two different flexible models are compared with data for the corresponding rigid SPC and SPC/E models. They found that the introduction of internal vibrations, and also their parametrization, has an observable effect on the prediction of the vapor-liquid coexistence curve. The flexible SPC/Fw model, although optimized to describe bulk diffusion and dielectric constants at ambient conditions, gives the best prediction of saturation densities and the critical point of the examined models. [ABSTRACT FROM AUTHOR]

We present a new thermodynamic integration method that directly connects the vapor and solid phases by a reversible path. The thermodynamic integration in the isothermal-isobaric ensemble yields the Gibbs free energy difference between the two phases, from which the sublimation temperature can be easily calculated. The method extends to the binary mixture without any modification to the integration path simply by employing the isothermal-isobaric semigrand ensemble. The thermodynamic integration, in this case, yields the chemical potential difference between the solid and vapor phases for one of the components, from which the binary sublimation temperature can be calculated. The coexistence temperatures predicted by our method agree well with those in the literature for single component and binary Lennard-Jones systems. [ABSTRACT FROM AUTHOR]

The liquid-vapor-phase equilibrium properties of the previously developed TIP4P-Ew water model have been studied using thermodynamic integration free-energy simulation techniques in the temperature range of 274–400 K. We stress that free-energy results from simulations need to be corrected in order to be compared to the experiment. This is due to the fact that the thermodynamic end states accessible through simulations correspond to fictitious substances (classical rigid liquids and classical rigid ideal gases) while experiments operate on real substances (liquids and real gases, with quantum effects). After applying analytical corrections the vapor pressure curve obtained from simulated free-energy changes is in excellent agreement with the experimental vapor pressure curve. The boiling point of TIP4P-Ew water under ambient pressure is found to be at 370.3±1.9 K, about 7 K higher than the boiling point of TIP4P water (363.7±5.1 K; from simulations that employ finite range treatment of electrostatic and Lennard-Jones interactions). This is in contrast to the approximately +15 K by which the temperature of the density maximum and the melting temperature of TIP4P-Ew are shifted relative to TIP4P, indicating that the temperature range over which the liquid phase of TIP4P-Ew is stable is narrower than that of TIP4P and resembles more that of real water. The quality of the vapor pressure results highlights the success of TIP4P-Ew in describing the energetic and entropic aspects of intermolecular interactions in liquid water. [ABSTRACT FROM AUTHOR]

An optimized molecular potential model for carbon dioxide is presented in this paper. Utilizing the established techniques of molecular-dynamics and histogram reweighting grand canonical Monte Carlo simulations, this model is demonstrated to show excellent predictability for thermodynamic, transport, and liquid structural properties in a wide temperature-pressure range with remarkable accuracies. The average deviations of this new model from experimental data for the saturated liquid densities, vapor densities, vapor pressures, and heats of vaporization are around 0.1%, 2.3%, 0.7%, and 1.9%, respectively. The calculated critical point is almost pinpointed by the new model. The experimental radial distribution functions ranging from 240.0 to 473.0 K are well reproduced as compared to neutron-diffraction measurements. The predicted self-diffusion coefficients are in good agreement with the nuclear-magnetic-resonance measurements. The previously published potential models for CO2 are also systematically evaluated, and our proposed new model is found to be superior to the previous models in general. [ABSTRACT FROM AUTHOR]

The heat of sublimation, density, melting point, and glass transition temperature are calculated for myo- and neo-inositol, using the condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASS) [H. Sun, J. Phys. Chem. B 102, 7338 (1998)] force field and molecular dynamics techniques. Our results show that the calculated heats of sublimation and density are very close to the experimental values for both compounds. Furthermore, our simulated melting temperatures for myo- and neo-inositol also compare very well to the experimentally obtained data. The glass transition temperatures for myo- and neo-inositol have been calculated to be ca. 494 K and ca. 518 K, respectively, and the shape of the volume versus temperature plots produced are typical for a glass transition. As a result, it is our view that the COMPASS force field suitably describes these two compounds in molecular simulations and that molecular dynamics techniques, combined with this force field, can be used to simulate the melt and glass transitions for such molecules. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We present an in-flight fluorescence detection scheme for molecular beams which is applied to determine the enthalpy of sublimation of dye molecules. We investigate tetraphenylporphyrin (TPP), porphine, and nile red, which are believed to be suitable candidates for molecular de Broglie wave interferometry [L. Hackermüller et al., Phys. Rev. Lett. 91, 090408, 2003]. The measured values are Hsub(TPP)=142±3 kJ/mol, Hsub(porphine)=87±3 kJ/mol, and Hsub(nile red)=66±2 kJ/mol. For TPP, sublimation enthalpies differ in the literature by more than a factor of 2. Our measurements confirm a value at the lower end of this scale. We discuss changes in the character of the molecular flow with the source temperature as a prime reason for discrepancies in the published data. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Nascent quantum states of CO2 subliming from CO2 thin films at rates of 1 to 103 monolayers (ML) per second are probed via direct infrared absorption of the ν3 asymmetric stretch with a frequency ramped diode laser. The high spectral resolution (Δν≊15 MHz) of the diode laser and the use of polarization modulation techniques permit individual rotational, vibrational, translational, and even MJ degrees of freedom of the subliming flux to be studied with quantum state resolution. Measured rotational and ν2 bend vibrational distributions indicate that the molecules sublime from the surface in a Boltzmann distribution characterized by the thin film temperature Ts. Similarly, the velocity distributions parallel to the surface are well described by a Maxwell velocity distribution at Ts, as determined by high resolution Doppler analysis of the individual rovibrational line shapes. The MJ distribution of subliming rotational states is probed via polarization modulation methods; no alignment is detected within experimental sensitivity. This places an upper limit on the anisotropy in the rotational distribution of |n⊥/n||-1|<0.02, where n⊥/n|| is the ratio of molecules with J perpendicular vs parallel to the surface normal. By virtue of the direct absorption technique, the absolute sublimation rates from the surface can be obtained from the measured column integrated densities. Via detailed balance, these fluxes are compared with equilibrium vapor pressure measurements to retrieve the absolute sticking coefficients S for gas phase CO2 impinging on a solid phase CO2 thin film. For sublimation rates <103 ML/s, the data indicate S=1.0±0.2, irrespective of quantum state, rotational alignment, and tangential velocity component. For sublimation rates >=103 ML/s, the onset of a mild supersonic expansion is observed, with post-desorption collisions cooling the rotational temperature by as much as 15 K below Ts. Modeling of the... [ABSTRACT FROM AUTHOR]

Using Knudsen effusion mass spectrometry, we have identified the following reaction as the sublimation decomposition mechanism of NpO2F2(s): 2NpO2F2(s)=NpO2(s)+O2(g)+NpF4(g). From second-law analysis of the measured pressures of NpF4(g) over the temperature range 820–985 K the derived enthalpy change at 298 K is 556.8±12.2 kJ/mol and the entropy change is 342.4 ±13.8 J/K mol. From these values and enthalpies of formation and entropies reported in the literature for the other species we calculate the enthalpy of formation of NpO2F2(s) to be -1608±10 kJ/mol and the entropy to be 147±9 J/K mol. [ABSTRACT FROM AUTHOR]

The sublimation entropies of the thorium and uranium tetrahalides (except UI4 ) have been evaluated from torsion–effusion vapor pressure measurements and the results have been analyzed for compatibility with the spectroscopic and molecular constants of the gaseous molecules. New effusion pressure measurements are reported here for UCl4, UBr4, and ThI4. For UF4, UCl4, and ThF4, where thermal data are available for the solid phases, the experimental entropies of gaseous UF4 and UCl4 are incompatible with regular tetrahedral symmetries, while that of ThF4 is in close accord with a Td structure. A comparison of the entropies of sublimation shows that ThCl4 most likely has Td symmetry, while UBr4, ThBr4, and ThI4 probably do not; less-reliable total entropy data for the species are in full accord with these conclusions. The results are discussed in terms of structural information in the literature. [ABSTRACT FROM AUTHOR]

The enthalpy of sublimation of fermium (Fm), element 100, has now been determined directly by measuring the partial pressure of Fm over alloys, for the temperature range of 642 to 905 K. The partial pressures were determined using Knudsen effusion and target collection techniques. Dilute (10-5–10-7 atom %) solid alloys of Fm and mixtures of Fm and Es in both Sm and Yb solvents were studied. The presence of Es in two of the alloys allowed a direct comparison of the behavior of Fm and Es, where the latter could be used as a reference. It was possible to calculate enthalpies of sublimation and a hypothetical vapor pressure/temperature relationship for pure Fm metal by selecting Yb as the solvent most likely to form a nearly ideal alloy with Fm. From the experimental vapor pressure data, we derived average Second Law values of 33.8±3 kcal/mol and 23.5±3 cal/mol deg for the enthalpy and entropy of sublimation of Fm at 298 K. Third Law enthalpy values were also calculated using the experimental partial pressure data and entropies estimated from derived free energy functions and heat capacities for the solid and gaseous forms of Fm. The average Third Law values (34.8 kcal/mol and 25.1 cal/mol deg, respectively, at 298 K) are in agreement with those obtained via the Second Law. These results establish that Fm, like Es (element 99), is a divalent metal. The finding that Fm metal is the second divalent actinide element experimentally establishes the trend towards metallic divalency expected in the second half of the actinide series. [ABSTRACT FROM AUTHOR]

Investigates the thermodynamic properties of the gaseous dimer of CdI[sub 2]. Use of the Knudsen effusion mass spectroscopy; Determination of the dimer content in the equilibrium vapor; Evaluation of the enthalpies of the sublimation and dissociation process.

Calculations are reported of properties of solid and fluid phases of the Xe/Ag(111) monolayer. The thermal expansion of the solid at its sublimation curve is calculated and the monolayer triple point is estimated. Anharmonic effects in the solid are discussed and mean field approximations to the adsorption dipoles in the dense fluid are introduced. The interaction model reproduces the low temperature properties of the monolayer solid, but there are small departures from the experimental data for the thermal expansion above 60 K. The calculated triple point temperature is significantly lower than the values reported for other monolayer xenon systems. [ABSTRACT FROM AUTHOR]

Molecular dynamics methods have been employed in order to calculate the (p,ρ,T)-properties and the internal energy of gas and crystal phases in stable and metastable equilibrium coexistence states for a model system consisting of 2048 Lennard-Jones particles. Thermal and caloric equations of state and the spinodal curves of the vapor and crystal phases have been determined. A new algorithm for the computation of phase equilibrium curves is suggested. Employing this method, the sublimation curve and its metastable extension to temperatures above the triple point have been calculated. It is found that the crystal-gas phase equilibrium terminates on the spinodal of the superheated crystal. The point of contact of the sublimation line and the spinodal is a singular point of the thermodynamic surface of states of a simple system considered. [ABSTRACT FROM AUTHOR]