Elastic anharmonicity of InP: Its relationship to the high pressure transition

Ultrasonic wave transit times have been measured in n-type InP at room temperature using hydrostatic pressures up to 4 kbar. Linear pressure dependences are found for the elastic stiffness moduli implying that at the high pressure structural-electrical transition the shear-to-bulk modulus ratio $\text{(C}{}_{11}\text{?C}{}_{12}\text{)}\text{2B}$ has a (fractional) value which fits the modified Born criterion for stability developed by Demarest $\text{et al}$. The anharmonic force constants and some of the third order elastic constants are found to be smaller the higher the transition pressure for indium III-V compounds.     

Excited vibrational state microwave spectra,structure, and force-field of trifluorosilane

The J = 2?1 microwave spectrum of six isotopic species of HSiF₃ has been observed and assigned in excited states of five of the six fundamental vibrations. The assignment is based on relative intensities, double resonance experiments, and trial anharmonic force constant calculations. Analysis of the spectra leads to experimental values for five of the $\text{α}{}_{\mathrm{r}}{}^{\mathrm{B}}$ constants, all three l-doubling constants q_t, one Fermi resonance constant φ₂₃₃, and one zeta constant $\text{ζ}{}_{\mathrm{6,\; 6}}{}^{\mathrm{(z)}}$.The harmonic force field has been refined to all the available data on vibration wavenumbers, centrifugal distortion constants, and zeta constants. The cubic anharmonic force field has been refined to the data on $\text{α}{}_{\mathrm{r}}{}^{\mathrm{B}}$ and q_t constants, using two models: a valence force model with two cubic force constants for SiH and SiF stretching, and a more sophisticated model. With the help of these calculations, the following equilibrium structure has been determined: $\text{r}{}_{\mathrm{e}}\text{(}\text{SiH}\text{) = 1.4468(±5)}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(}\text{SiF}\text{) = 1.5624(±1)}\text{A}\text{?}$, ∠HSiF = 110.64(±3)°,     

Anomalous temperature dependence of third-order elastic constants in NH4Cl and NH4Br near the λ point

Second order elastic constants of NH₄Cl and NH₄Br crystals were measured under hydrostatic and uniaxial pressures near the λ-type phase transitions. Third order elastic constants were calculated from the pressure derivatives of the second order elastic constants. Results show that the temperature dependences of the third order elastic constants of NH₄Cl differ from those of NH₄Br dramatically. In addition, it is found that the coefficients $\text{1}\text{54}\text{(C}{}_{111}\text{+ 6C}{}_{112}\text{+ 2C}{}_{123}\text{)}$ and $\text{(}\text{1}\text{24}\text{√3)(C}{}_{111}\text{? 3C}{}_{112}\text{+ 2C}{}_{123}\text{)}$ of strains in the free energy of NH₄Cl show quite different temperature dependences from those of NH₄Br.     

The elastic behaviour of the ternary zincblende structure semiconductor CuGe2P3

A single crystal has been grown of CuGe₂P₃, a ternary semiconductor with a zincblende structure in which the copper and germanium atoms are randomly distributed on the cation sites. The second order elastic constants measured by the ultrasonic pulse echo overlap technique (C₁₁ = 13.66, C₁₂ = 6.17, C₄₄ = 6.66 and bulk modulus B = 8.67 in units of 10¹⁰Nm^?2 at 291 K) are closely similar to those of GaP and conform well to Keyes' correlation for zincblende structure crystals. The hydrostatic pressure derivatives of the second order elastic constants ($\text{?C}{}_{11}\text{?P}\text{= 4.40}$, $\text{?C}{}_{12}\text{?P}\text{= 3.9}$, $\text{?C}{}_{44}\text{?P}\text{= 0.93}$ and $\text{?B}\text{?P}\text{= 4.07}$) and the third order elastic constants (C₁₁₁ = ? 8.45, C₁₁₂ = ? 3.49, C₁₂₃ = ? 1.13, C₁₄₄ = ? 2.82, C₁₅₅ = ? 1.44 and C₄₅₆ = ? 0.69 in units of 10¹¹Nm^?2) also resemble those of GaP: even the anharmonicity of the long wavelength acoustic modes of this ternary semiconductor resembles that of its binary “parent” compound. The positive signs of the hydrostatic pressure derivatives and the negative signs of the third order elastic constants show that the acoustic modes at the long wavelength limit stiffen under pressure, an effect which is quantified here by computation of the mode Grüneisen parameters, which are all positive. The harmonic and anharmonic force constants, obtained in the valence force field model, fit well into the pattern shown by related zincblende structure compounds: the ratio ($\text{β}\text{α}$) for bond bending (β) to stretching (α) force constants is greater than 4:1; the dominating anharmonic force constant is γ: most of the anharmonicity is associated with nearest neighbour atoms. Analysis of the temperature dependence of the elastic constants on the basis of a simple anharmonic model again emphasises the similarity between the elastic behaviour of CuGe₂P₃ and GaP. The thermal expansion of CuGe₂P₃ varies almost linearly with temperature between 291 K and 1000 K, the linear coefficient of thermal expansion α being 8.21 ± 0.02 × 10^?6 °C^?1. The similar lattice parameters and elastic behaviour of CuGe₂P₃ and GaP indicate that semiconducting devices made of epitaxial deposits of CuGe₂P₃ on a GaP substrate should prove to be almost strain-free.     

Elastic moduli and mode gammas of GaP: Their relationship to those of other isomorphic crystals and the high pressure structural-electrical transition

The transit times of ultrasonic waves associated with piezoelectrically inactive modes have been measured in sulfur-dope, n-type GaP using hydrostatic pressures up to 5 kbar. The velocities and elastic constants of most modes increase linearly with pressure but $\text{C}{}_{\mathrm{S}}\text{=}\text{1}\text{2}\text{(}\text{C}{}_{11}\text{?}\text{C}{}_{12}\text{)}$ decreases slightly. The behavior of the elastic constants and their associated mode gammas are compared to those of other III–V compounds and of Si and Ge. We suggest that the behavior of C_S is related to the occurrence of the structural-electrical transition which occurs at high pressure. A modified Born criterion for lattice stability developed by Demarest $\text{et}$$\text{al}$. is used to explain this relationship. The contribution of thermal dilatation to the temperature dependence of each elastic constant is deduced. Using it and data from the literature we find that the explicit thermal contribution to each elastic constant is significant and in the case of C₁₂ has an anomalous sign.     

Third and fourth order elastic constants of fluoperovskites CsCdF3, TlCdF3, RbCdF3, RbCaF3

The hydrostatic dependence of the second order elastic constants of several fluoperovskites has been measured and studied from a macroscopic point of view and through a force field analysis. The first part of this paper is devoted to the experimental determination of some combinations of the third and fourth order elastic constants. The second part analyses the pressure dependence of the second order elastic constants from a macroscopic point of view. The large values of the second order anharmonicity coefficients $\text{b}{}_{\mathrm{ij}}\text{=}\text{1}\text{2}\text{(}\text{?}{}^2\text{C}{}_{\mathrm{ij}}\text{?P}{}^2\text{)}{}_0\text{C}{}^{\mathrm{(0)}}{}_{\mathrm{ij}}$ are connected to the occurrence of a phase transition in some compounds, whereas the first order coefficients $\text{(}\text{?C}{}_{\mathrm{ij}}\text{?P}\text{)}{}_0$ have an order of magnitude which agrees with a quasiharmonic hypothesis. The third part is devoted to the microscopic interpretation of the third order elastic constants. A rigid ion model is used with either classical Born Mayer potentials or a modification of these potentials with an axial term (Cowley and Rousseau's models).     

Microwave spectrum of acetylene-d2

Eight P-branch transitions from the $\text{ν}{}_5{}^1\text{-ν}{}_4{}^1$ difference band of C₂D₂ have been observed in the microwave region. Significant improvements in the spectroscopic constants for the two states involved in the difference band have been obtained by combining infrared and microwave data. The Stark shifts for the observed C₂D₂ lines are discussed in some detail. The vibrational transition moment is found to be μ_vib = 0.0358 ± 0.0020 D.     

The microwave spectrum of 2,4-dioxabicyclo[3.1.0]hexan-3-one

The R band (26.5–40 GHz) microwave spectrum of 2,4-dioxabicyclo[3.1.0]hexan-3-one is reported. Rotational constants for the ground vibrational state of the common ¹²C₄¹H₄¹⁶O₃ and ¹³C₁, ¹³C₆ isotopically substituted species (the latter observed in natural abundance) have been evaluated. In addition rotational constants of the V_B = 1 to V_B = 5 quanta associated with the bending vibration of the five membered ring have been determined. A partial r_s structure has been calculated:

$\text{r(}\text{C}{}_1\text{?}\text{C}{}_5\text{) = 1.497± 0.016}\text{A}\text{?}\text{, r(}\text{C}{}_1\text{?}\text{C}{}_6\text{) = r(}\text{C}{}_6\text{?}\text{C}{}_5\text{) = 1.522 ± 0.015}\text{A}\text{?}$

,

$\text{∠}\text{C}{}_6\text{C}{}_1\text{C}{}_5\text{= ∠}\text{C}{}_1\text{C}{}_5\text{C}{}_6\text{= 60°32′ ± 1°36′, ∠}\text{C}{}_1\text{C}{}_6\text{C}{}_5\text{= 58°′ ± 1°47′}$

. With certain assumed molecular information a least squares fit yields the following parameters:

$\text{β = 68.5 ± 0.02°, r(}\text{C}{}_1\text{O}{}_2\text{= 1.408 ± 0.004}\text{A}\text{?}$

,

$\text{∠}\text{C}{}_5\text{C}{}_1\text{O}{}_2\text{= 105.8 ± 0.02°, ∠}\text{C}{}_1\text{O}{}_2\text{C}{}_3\text{= 108.10 ± 0.03°}$

,

$\text{∠}\text{O}{}_2\text{C}{}_3\text{O}{}_4\text{= 112.8 ± 0.02°}$

.     

The anharmonic force field of phosphorus trifluoride from the millimeter wave spectra of vibrationally excited states

The millimeter rotational spectra of PF₃ have been recorded for all four excited fundamental vibrational states. A coriolis resonance between ν₁ and ν₃ results in anomalous distortion constants for these states and can be analyzed to yield $\text{|ζ}{}_{13}{}^{\mathrm{y}}\text{| = 0.392}$. The value of $\text{ζ}{}_{33}{}^{\mathrm{c}}$ is found to be 0.4194 which does not fit the coriolis sum rule due to anharmonic resonance. Equilibrium values for the centrifugal distortion constants are determined and have been used to find the harmonic force field. All available data is used to determine some of the anharmonic force constants.     

A numerical estimate of deviations from the exponential decay law for the transition 2P12→1S12 in hydrogen

The deviations from the exponential decay law of the $\text{2}\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ states of the Dirac hydrogen atom with respect to the transition $\text{2}\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{→1}\text{S}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ are numerically estimated. We find |a₀(t) ? exp(?λt)|?2.5 × 10^?4 for all t, where a₀(t) is the “exact” decay amplitude and λ is a complex constant such that (2Re λ)^?1 is the “natural lifetime” of the $\text{2}\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ states with respect to the spontaneous transition to $\text{1}\text{S}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$.     

Light scattering study of dispersion and attenuation of hypersound in adamantane

The Brillouin scattering techniques have been used to measure the velocity dispersion of hypersonic acoustic waves in the “high temperature” disordered cubic phase of adamantane. Shear waves, characteristic of the C₄₄ elastic constant, show no significant dispersion. Longitudinal waves propagating in the (001) plane show strong velocity dispersion. The measures have been performed at the same temperature T = 295.7 K. Using a classical single relaxation time model for the dispersion as a function of frequency at temperature T, the L-mode data have been correctly fitted.The importance of the dispersion $\text{(C}{}_{\mathrm{\infty }}\text{? C}{}_{\mathrm{o}}\text{)}\text{C}{}_0$ for the elastic constants is 20% for C₁₁, 51% for C₁₂ #1% for C₄₄ and ?2.8% for $\text{(C}{}_{11}\text{? C}{}_{12}\text{)}\text{2}$. The fitted relaxation time is τ ? 9 × 10^?11 sec.     

CLL = (L,L; 0, 0) measurements and a structure due to a P partial wave in the pp system

Measurements of C_LL of pp elastic scattering near θ_c.m. = 90° at thirteen energies between 300 and 800 MeV are reported. These, together with previous values of C_NN, are used to extract values of two quantities, $\text{?}{}_{\mathrm{<mtext>s</mtext>}}$ and $\text{?}{}_{\mathrm{<mtext>t</mtext>}}$, which contain only spin-singlet and only coupled spin-triplet partial waves, respectively. The $\text{?}{}_{\mathrm{<mtext>s</mtext>}}$ curve, which is not dependent on C_LL, exhibits the behavior expected for the previously conjectured ¹D₂ resonance. The $\text{?}{}_{\mathrm{<mtext>t</mtext>}}$ curve also exhibits a resonance-like behavior, which could be due either to the ³P₀ or the ³P₂ partial wave.     

The renormalization of the string operator in QCD

We shall observe that the renormalization of the string operator U(x₁, x₂; C) = Pexp{ig∫_x1^x2dx_μA^μ(x)} with an open path C (smooth and non-intersecting) is path-independently performed in any order of perturbation. To demonstrate this, the renormalization constants will be calculated up to order g⁴. Next the renormalization effect on the algebraic identity $\text{U(x}{}_1\text{, x}{}_2\text{;}\text{C}\text{)U(x}{}_2\text{, x}{}_3\text{;}\text{C}\text{) = U(x}{}_1\text{, x}{}_3\text{;}\text{C}\text{∪}\text{C}\text{)}$ will be discussed and it will be proved that the renormalization preserves the algebraic identity in any order of perturbation if the paths C and $\text{C}$ are smoothly connected at x₂. Finally, the string operator renormalization is extended to the case when the path C is smoothly closed (the Wilson loop operator). It is then shown that the renormalization factor which multiplicatively renormalizes the string operator in the case of the open path, is cancelled in any order of perturbation by the divergence appearing in the coincidence of the end points. As a results, the Wilson loop operator can be renormalized by the coupling constant renormalization alone.     

Infrared-radio frequency double resonance observations of pure rotational Q-branch transitions of methane

The $\text{F}{}_2{}^{\mathrm{(2)}}\text{← F}{}_1{}^{\mathrm{(2)}}$ and $\text{F}{}_2{}^{\mathrm{(2)}}\text{← F}{}_1{}^{\mathrm{(1)}}$ transitions of the J = 7 levels of the ground state of CH₄ have been observed by infrared-radio frequency double resonance using the 3.39 μ HeNe laser line. The transition frequencies are 423.02 ± 0.02 MHz and 1246.55 ± 0.02 MHz, respectively. Using these frequencies and the splitting of the E and F₂ levels of the J = 2 state calculated from the molecular beam magnetic resonance spectra of Ozier, the centrifugal distortion constants are derived to be D_t = 132933 ± 10 Hz, H_4t = ? 16.65 ± 0.2 Hz, and H_6t = 10 ± 1 Hz. The J = 15 E⁽¹⁾ → E⁽²⁾ microwave transition is predicted as 14150 ± 9 MHz.     

Information on the dynamics of the reaction KN → K1N from KLN interactions

If $\text{K}{}_{\mathrm{S}}{}^1\text{,}{}_{\mathrm{L}}\text{is a K}{}^1$ resonance decaying into K_S,L (the short- and long-lived kaon) and a neutral system S^o of pions, one can isolate the C-even and C-odd, crossed-channel contributions to $\text{KN → K}{}^1\text{N}$ by using the reactions $\text{K}{}_{\mathrm{L}}\text{N → K}{}_{\mathrm{S}}{}^1\text{,}{}_{\mathrm{L}}\text{N}$ whether S^o is a C-eigenstate, or a mixture of C-even and C-odd states. Applications to the production of K¹(890) and the Q-meson are discussed, and simple numerical predictions made for Q_S,L production. Q-production data indicate approximate t-channel helicity conservation for the ω and P' exchanges at vertices involving a spin change, in similarity to the belief for the pomeron. Q_S,L production data can give information also on Q-decays.     

Elastic constant pressure derivatives and stability of the bcc phase of InTl alloys

Hydrostatic-pressure derivatives of the elastic stiffness constants have been measured ultrasonically in a bcc InTl alloy of composition near the eutectoid. The shear modulus $\text{1}\text{2}\text{(C}{}_{11}\text{?C}{}_{12}\text{)}$ is small, but does not soften under pressure: the eutectoid reaction is not directly associated with a mode softening shear instability. Anharmonic contributions to the excess vibrational entropy from the q 〈110〉, e 〈1$\text{1}$0〉 modes which stabilize the bcc structure are small compared with the harmonic contributions.     

Study by brillouin scattering of the C33 constant of thiourea submitted to an electric field

The C₃₃ constant is discontinuous for the lock-in transition at T₁ = 169 K. The variation ΔT₁ of the temperature of transition is a linear function of the applied electric field E and we find $\text{d}\text{T}{}_1\text{d}\text{E}\text{=0.82 deg.cm kV}{}^{\mathrm{?1}}$.Above a mean field E = 10 kV cm^?1 the transition observed for a first heating spreads on several degrees because damages appear in the incommensurate phase and the electric field becomes inhomogeneous.The results obtained at low fields are in very good accordance with the value of $\text{d}\text{T}{}_1\text{d}\text{E}$ calculated from the Clapeyron formula.Taking into account of the incommensurability of the phase above T₁, it can be shown that

$\text{dT}{}_1\text{dE}\text{=}\text{C}\text{2πP}{}_{\mathrm{o}}\text{3}\text{3}\text{?}\text{2}$

The knowledge of the spontaneous polarisation P₀ gives for the Curie constant C = 2.1 × 10³ K in qualitative agreement with the value deduced from measurements of the dielectric constant in the ferroelectric direction.     

The influence of excess oxygen on the elastic properties of non-stoichiometric SrO crystals

Measurements have been carried out of the elastic constants of SrO in the virgin undoped state and of the changes produced in them by equilibrium doping with oxygen at ? 1200°C and oxygen partial pressure of 0.95 atm. The method used was Papadakis' pulse-echo overlap technique in conjunction with thermogravimetric analysis (T.G.A.) to determine mass and density changes due to oxygen doping.The values obtained for C₁₁, C₁₂ and C₄₄ of the virgin crystal at 23°C are

$\text{C}{}_{11}\text{= 17.60 ± 0.03 × 10}{}^{11}\text{dynes/cm}{}^2$

;

$\text{C}{}_{12}\text{= 4.808 ± 0.007 × 10}{}^{11}\text{dynes/cm}{}^2$

;

$\text{C}{}_{44}\text{= 5.577 ± 0.008 × 10}{}^{11}\text{dynes/cm}{}^2$

.(These values are in very good agreement with those of Son and Bartels [2].)Values for $\text{δC}{}_{11}\text{C}{}_{11}$ and $\text{δC}{}_{44}\text{C}{}_{44}$ were found to be ?1.74% and ?0.86% respectively. Accurate valu $\text{δC}{}_{12}\text{C}{}_{12}$ could not be obtained because of sample size limitations after quenching. However, C₁₂ was shown to definitely increase due to doping.Analysis of the results indicate that the elastic modulus changes can only be attributed to the formation of cation vacancies during doping. Analysis of the T.G.A. behavior indicates that this cation vacancy formation is probably associated with the presence of various tripositive cation and uninegative anion species depending upon the impurity concentrations of the sample. This implied impurity-controlled cation vacancy concentration is consistent with the earlier observed extrinsic nature of cation diffusion in SrO at 1200°C.     

An anharmonic force field for SO3

An anharmonic force field for SO₃ based on the valence force model has been investigated. The results of extending the model to include some further estimated cubic interaction potential constants have also been investigated. The phenomenological parameters calculated from both model force fields agree with those few values which have been experimentally determined. A calculation of the inertia defect has been made, and thus the value of C₀ has been determined. The equilibrium structure has been determined to be: $\text{r}{}_{\mathrm{e}}\text{= 1.4184 ± 0.0010}\text{A}\text{?}$.