Calculation of force constants and mean amplitudes of vibration of octahedral XY6 molecules using frequencies and zeta constants

Expressions involving vibrational frequencies, Coriolis coupling constants and masses of the atoms of the molecule that are invariant under symmetrical isotopic substitutions are derived for octahedral XY₆ molecules following the method given by Jagannathan and others. These invariants are used to calculate the force constants, compliance constants and mean amplitudes of vibration of 13 molecules of XY₆-type.     

meso-四(4-磺基苯基)卟啉(TPPS)在微乳液中的行为研究

本文首次研究了ｍｅｓｏ－四（４－磺基苯基）卟啉（ＴＰＰＳ）在Ｏ／Ｗ型微乳液（Ｔｒｉｔｏｎ Ｘ－１００－壬烷－正戊醇－水）体系中的电子吸收光谱变化，计算了ＴＰＰＳ的电离常数Ｋａ及二聚常数ＫＤ。     

An Improved Anharmonic Force Field of Difluoromethanimine, F2C NH

The anharmonic force field of difluoromethanimine, F₂C NH, has been reinvestigated theoretically using a coupled-cluster singles and doubles approach, augmented for structural optimization and harmonic force field by a contribution of connected triple excitations, CCSD(T). The cubic and quartic force constants have been obtained by numerical derivatives computed from analytical quadratic force constants calculated by second-order Møller-Plesset perturbation theory, MP2. The quadratic force constants and the equilibrium structure of F₂C NH have then been scaled by a global least-squares fitting procedure to the spectroscopic data and parameters experimentally determined for this molecule. This force field, obtained in the internal coordinates space and therefore valid for all isotopomers of difluoromethanimine, yields a complete set of spectroscopic molecular constants providing a critical assessment of the experimental rotational and centrifugal distortion constants, fundamentals, overtones, and combination bands determined so far for F₂C NH. In addition, the final force field can be used to make predictions of all important vibrational and rotational parameters which should be accurate and useful for new spectroscopic investigations.     

Ultrasonic wave propagation in rare-earth monochalcogenides

The ultrasonic attenuation in thulium monochalcogenides TmX (X=S, Se and Te) has been studied theoretically with a modified Mason’s approach in the temperature and range 100 K to 300 K along 〈100〉, 〈110〉 〈111〉 crystallographic directions. The thulium monochalcogenides have attracted a lot of interest due to their complex physical and chemical characteristics. TmS, TmSe and TmTe are trivalent metal, mixed valence state, and divalent semiconductor, respectively. Coulomb and Born-Mayer potential is applied to evaluate the second- and third-order elastic constants. These elastic constants are used to compute ultrasonic parameters such as ultrasonic velocities, thermal relaxation time, and acoustic coupling constants that, in turn, are used to evaluate ultrasonic attenuation. A comparison of calculated ultrasonic parameters with available theoretical/experimental physical parameters gives information about classification of these materials.      

GeS分子基态和低激发态的势能曲线与光谱性质

本文以aug-cc-pv5Z为基组, 采用考虑Davidson修正的多参考组态相互作用方法(MRCI+Q)得到了GeS分子基态(X¹Σ⁺)和5个低激发态(1¹Σ, 1¹Δ, A¹Π, 1⁵Σ⁺, 2⁵Σ⁺)的势能曲线. 计算结果表明: 2⁵Σ⁺态为排斥态, 其余5个态为束缚态; 6个态有着共同的离解通道, 离解极限均为Ge(³P)+S(³P). 利用计算得到的势能曲线得了X¹Σ⁺, 1¹Σ^-, 1¹Δ, A¹Π和1⁵Σ⁺态的垂直跃迁能T_e, 平衡键长R_e, 离解能D_e, 谐振频率ω_e, 非谐性常数ω_ex_e及平衡位置的电偶极矩. X¹Σ⁺态的R_e 为2.034 Å, D_e 为5.728 eV, ω_e为571.73 cm^-1, ω_ex_e为1.6816 cm^-1, 平衡位置的电偶极矩为1.9593 Debye. 激发态1¹Σ, 1¹Δ, A¹Π, 1⁵Σ⁺的T_e 依次为25904.81, 26209.22, 32601.19, 43770.26 cm^-1; R_e依次为2.313, 2.322, 2.188, 2.8790 Å; D_e依次为2.524, 2.487, 1.694, 0.3036 eV, ω_e依次为358.90, 353.08, 376.32, 134.96 cm^-1; ω_ex_e依次为1.2421, 1.2151, 1.6608, 1.9095 cm^-1; 平衡位置的电偶极矩依次为1.3178, 1.4719, 1.5917, -1.9785 Debye. 通过求解核运动的薛定谔方程得到了J=0时X¹Σ⁺, 1¹Σ^-, 1¹Δ, A¹Π和1⁵Σ⁺态前30个振动态的振动能级G_v和分子常数B_v, 得到的结果和已有的实验值及其他理论值符合较好.     

Xenon saturation spectroscopy by diode laser

Summary Commercial diode lasers have emission wavelengths which overlap some absorption xenon lines. We have performed saturation spectroscopy of four lines, leaving from the first excited atomic configuration 5p ⁵6s, at 823.16 nm, at 828.01 nm, at 834.68 nm and at 820.63 nm, in a weak glow discharge of natural xenon. Natural xenon is a mixture of several isotopes, and the two even isotopes, Xe(129) (26% of relative abundance) and Xe(131) (21%), have a nuclear spin (1/2 and 3/2, respectively) that produces a hyperfine structure. The complex resulting spectra have been resolved and the results are compared with the available literature data. The authors of this paper have agreed to not receive the proofs for correction.     

Polarization spectroscopy of atomic oxygen by dye and semiconductor diode lasers

Summary We used polarization spectroscopy to perform a high-resolution investigation of atomic oxygen in the visible and near-infrared spectral region by means of dye and semiconductor diode lasers. We measured the fine structure of the highly excited 4d ⁵ D level and resolved the hyperfine structure of the metastable 3s ⁵ S ₂ level of¹⁷O. Isotope shift values are also reported for several transitions of the three stable oxygen isotopes (¹⁶O,¹⁷O,¹⁸O). Polarization lineshapes are discussed and compared with those obtained in saturation techniques.     

Study of ππ final state interactions in ψ(2S)→π+π-J/ψ

The π+π- transition of heavy quarkonia in decay ψ(2S) ψ(2S)→π+π-J/ψ is studied. With the BESII data on the decay ψ(2S)→π+π-J/ψ, we update the values of coupling constants (gi) and chromopolarizability (аψ(2S)J/ψ) in this process.     

Relational Evolution of the Degrees of Freedom of Generally Covariant Quantum Theories

We study the classical and quantum dynamics of generally covariant theories with vanishing Hamiltonian and with a finite number of degrees of freedom. In particular, the geometric meaning of the full solution of the relational evolution of the degrees of freedom is displayed, which means the determination of the total number of evolving constants of motion required. Also a method to find evolving constants is proposed. The generalized Heisenberg picture needs M time variables, as opposed to the Heisenberg picture of standard quantum mechanics where one time variable t is enough. As an application, we study the parametrized harmonic oscillator and the SL(2, R) model with one physical degree of freedom that mimics the constraint structure of general relativity where a Schrödinger equation emerges in its quantum dynamics.     

Anharmonic force constants of GaSb from the measured third order elastic constants at 300°K

The third-order elastic constants of single crystal GaSb are determined using ultrasonic pulse interferometer at 10 MHz. The constants at 300°K, in units of 10¹¹ N.m.⁻², are C_l11 = ™ 4 ·75 ± 0·06 C₁₄₄ = + 0·50 ± 0·25 C₁₁₃ = ™ 3 ·08 ± 0·02 C₁₆₆ = ™ 2·16 ± 0·13 C₁₂₃ = ™ 0 ·44 ± 0·29 C₄₅₆ = ™ 0·25 ± 0·15 These constants are used to evaluate the three anharmonic first and second neighbour force constants based on modified Keating’s model. The constants are (in units of 10¹¹ N.m⁻²)γ=− 2·406;δ=0·407;ε=−0·222.