Pressure Tuning of the Charge Density Wave in the Halogen-Bridged Transition-Metal (MX) Solid Pt2Br6(NH3)4Pt_2Br_6(NH_3)_4

We report the pressure dependence up to 95 kbar of Raman active stretching modes in the quasi-one-dimensional MX chain solid $Pt_2Br_6(NH_3)_4$. The data indicate that a predicted pressure-induced insulator-to-metal transition does not occur, but are consistent with the solid undergoing either a three-dimensional structural distortion, or a transition from a charge-density wave to another broken-symmetry ground state. We show that such a transition cacan be well-modeled within a Peierls-Hubbard Hamiltonian. 1993 PACS: 71.30.+h, 71.45.Lr, 75.30.Fv, 78.30.-j, 81.40.VwComment: 4 pages, ReVTeX 3.0, figures available from the authors on request (Gary Kanner, [email protected]), to be published in Phys Rev B Rapid Commun, REVISION: minor typos corrected, LA-UR-94-246

Free energy and molecular dynamics calculations for the cubic-tetragonal phase transition in zirconia

The high-temperature cubic-tetragonal phase transition of pure stoichiometric zirconia is studied by molecular dynamics (MD) simulations and within the framework of the Landau theory of phase transformations. The interatomic forces are calculated using an empirical, self-consistent, orthogonal tight-binding (SC-TB) model, which includes atomic polarizabilities up to the quadrupolar level. A first set of standard MD calculations shows that, on increasing temperature, one particular vibrational frequency softens. The temperature evolution of the free energy surfaces around the phase transition is then studied with a second set of calculations. These combine the thermodynamic integration technique with constrained MD simulations. The results seem to support the thesis of a second-order phase transition but with unusual, very anharmonic behaviour above the transition temperature

Engineered swift equilibration of a Brownian particle

A fundamental and intrinsic property of any device or natural system is its relaxation time relax, which is the time it takes to return to equilibrium after the sudden change of a control parameter [1]. Reducing $tau$ relax , is frequently necessary, and is often obtained by a complex feedback process. To overcome the limitations of such an approach, alternative methods based on driving have been recently demonstrated [2, 3], for isolated quantum and classical systems [4--9]. Their extension to open systems in contact with a thermostat is a stumbling block for applications. Here, we design a protocol,named Engineered Swift Equilibration (ESE), that shortcuts time-consuming relaxations, and we apply it to a Brownian particle trapped in an optical potential whose properties can be controlled in time. We implement the process experimentally, showing that it allows the system to reach equilibrium times faster than the natural equilibration rate. We also estimate the increase of the dissipated energy needed to get such a time reduction. The method paves the way for applications in micro and nano devices, where the reduction of operation time represents as substantial a challenge as miniaturization [10]. The concepts of equilibrium and of transformations from an equilibrium state to another, are cornerstones of thermodynamics. A textbook illustration is provided by the expansion of a gas, starting at equilibrium and expanding to reach a new equilibrium in a larger vessel. This operation can be performed either very slowly by a piston, without dissipating energy into the environment, or alternatively quickly, letting the piston freely move to reach the new volume

First-principles study of the ferroelastic phase transition in CaCl_2

First-principles density-functional calculations within the local-density approximation and the pseudopotential approach are used to study and characterize the ferroelastic phase transition in calcium chloride (CaCl_2). In accord with experiment, the energy map of CaCl_2 has the typical features of a pseudoproper ferroelastic with an optical instability as ultimate origin of the phase transition. This unstable optic mode is close to a pure rigid unit mode of the framework of chlorine atoms and has a negative Gruneisen parameter. The ab-initio ground state agrees fairly well with the experimental low temperature structure extrapolated at 0K. The calculated energy map around the ground state is interpreted as an extrapolated Landau free-energy and is successfully used to explain some of the observed thermal properties. Higher-order anharmonic couplings between the strain and the unstable optic mode, proposed in previous literature as important terms to explain the soft-phonon temperature behavior, are shown to be irrelevant for this purpose. The LAPW method is shown to reproduce the plane-wave results in CaCl_2 within the precision of the calculations, and is used to analyze the relative stability of different phases in CaCl_2 and the chemically similar compound SrCl_2.Comment: 9 pages, 6 figures, uses RevTeX

Magnetization steps in a diluted Heisenberg antiferromagnetic chain: Theory and experiments on TMMC:Cd

A theory for the equilibrium low-temperature magnetization M of a diluted Heisenberg antiferromagnetic chain is presented. The magnetization curve, M versus B, is calculated using the exact contributions of finite chains with 1 to 5 spins, and the "rise and ramp approximation" for longer chains. Some non-equilibrium effects that occur in a rapidly changing B, are also considered. Specific non-equilibrium models based on earlier treatments of the phonon bottleneck, and of spin flips associated with cross relaxation and with level crossings, are discussed. Magnetization data on powders of TMMC diluted with cadmium [i.e., (CH_3)_4NMn_xCd_(1-x)Cl_3, with 0.16<=x<=0.50 were measured at 0.55 K in 18 T superconducting magnets. The field B_1 at the first MST from pairs is used to determine the NN exchange constant, J, which changes from -5.9 K to -6.5 K as x increases from 0.16 to 0.50. The magnetization curves obtained in the superconducting magnets are compared with simulations based on the equilibrium theory. Data for the differential susceptibility, dM/dB, were taken in pulsed magnetic fields (7.4 ms duration) up to 50 T, with the powder samples in a 1.5 K liquid-helium bath. Non-equilibrium effects, which became more severe as x decreased, were observed. The non-equilibrium effects are tentatively interpreted using the "Inadequate Heat Flow Scenario," or to cross-relaxation, and crossings of energy levels, including those of excited states.Comment: 16 pages, 14 figure

Wafer-Scale, Sub-5 nm Junction Formation by Monolayer Doping and Conventional Spike Annealing

We report the formation of sub-5 nm ultrashallow junctions in 4 inch Si wafers enabled by the molecular monolayer doping of phosphorous and boron atoms and the use of conventional spike annealing. The junctions are characterized by secondary ion mass spectrometry and non-contact sheet resistance measurements. It is found that the majority (~70%) of the incorporated dopants are electrically active, therefore, enabling a low sheet resistance for a given dopant areal dose. The wafer-scale uniformity is investigated and found to be limited by the temperature homogeneity of the spike anneal tool used in the experiments. Notably, minimal junction leakage currents (<1 uA/cm2) are observed which highlights the quality of the junctions formed by this process. The results clearly demonstrate the versatility and potency of the monolayer doping approach for enabling controlled, molecular-scale ultrashallow junction formation without introducing defects in the semiconductor.Comment: 21 pages, 5 figure

Vitamin D Binding Protein and Monocyte Response to 25-Hydroxyvitamin D and 1,25-Dihydroxyvitamin D: Analysis by Mathematical Modeling

Vitamin D binding protein (DBP) plays a key role in the bioavailability of active 1,25-dihydroxyvitamin D (1,25(OH)2D) and its precursor 25-hydroxyvitamin D (25OHD), but accurate analysis of DBP-bound and free 25OHD and 1,25(OH)2D is difficult. To address this, two new mathematical models were developed to estimate: 1) serum levels of free 25OHD/1,25(OH)2D based on DBP concentration and genotype; 2) the impact of DBP on the biological activity of 25OHD/1,25(OH)2D in vivo. The initial extracellular steady state (eSS) model predicted that 50 nM 25OHD and 100 pM 1,25(OH)2D), <0.1% 25OHD and <1.5% 1,25(OH)2D are ‘free’ in vivo. However, for any given concentration of total 25OHD, levels of free 25OHD are higher for low affinity versus high affinity forms of DBP. The eSS model was then combined with an intracellular (iSS) model that incorporated conversion of 25OHD to 1,25(OH)2D via the enzyme CYP27B1, as well as binding of 1,25(OH)2D to the vitamin D receptor (VDR). The iSS model was optimized to 25OHD/1,25(OH)2D-mediated in vitro dose-responsive induction of the vitamin D target gene cathelicidin (CAMP) in human monocytes. The iSS model was then used to predict vitamin D activity in vivo (100% serum). The predicted induction of CAMP in vivo was minimal at basal settings but increased with enhanced expression of VDR (5-fold) and CYP27B1 (10-fold). Consistent with the eSS model, the iSS model predicted stronger responses to 25OHD for low affinity forms of DBP. Finally, the iSS model was used to compare the efficiency of endogenously synthesized versus exogenously added 1,25(OH)2D. Data strongly support the endogenous model as the most viable mode for CAMP induction by vitamin D in vivo. These novel mathematical models underline the importance of DBP as a determinant of vitamin D ‘status’ in vivo, with future implications for clinical studies of vitamin D status and supplementation