Rydberg states and ionization potentials of GeX,SnX, and PbX (X = F,Cl, Br,I)

Thirty-nine unattributed electronic states of group IV monohalides have been interpreted in terms of Rydberg configurations. Ionization potential and quantum defects have been derived.     

Electronic excitation of HgX (X = Cl,Br, I) due to electron and methyl mercury halide collisions

Electronic excitation of HgX (X = Cl, Br, I) radicals in the B-state has been observed as the result of collisions with low energy electrons and methyl mercury halide (CH₃HgX) molecules. The emission intensity has been observed to be much weaker than that observed for electron-HgX₂ collisions under similar experimental conditions. Using the strongest band head of the B-X band system, an attempt has been made to calculate the emission cross section due to electron CH₃HgX collisions at 10 eV electron kinetic energy. For HgCl, HgBr, and HgI radicals, these cross sections are 1 × 10^-18, 7 × 10^-17, and 2 × 10^-17 cm², respectively, with an estimated uncertainty of ±30%. Our measured threshold electron energy for excitation of CH₃HgX molecules and observation of the B-X emission band system and emission cross sections measured at 10 eV are greatly different from those measured by Allision and Zare [Chem. Phys. 35, 263 (1978)].     

Molecular Rydberg transitions: The lowest-energy Rydberg transitions of s-type in CH3X and CD3X,X = Cl,Br, and I

The absorption spectra associated with transitions to the lowest-energy s-type Rydberg states of CH₃X and CD₃X, X = Cl, Br, and I, have been measured and analyzed. The spectra of the bromides and iodides consist, individually, of four electronic origins of s-excitation type. The vibrational frequency of a given normal mode is more or less identical in all four excited states of any one molecule; and the excited state/ground state ratios of the frequencies of any given normal vibrational mode are essentially identical for all four molecules (i.e., for 16 states, four for each of two bromides and two iodides). The spectra of the chlorides are amenable to a number of different vibronic analyses, none of them unique; these analyses are discussed.     

Structural and magnetic phase transitions in (Chloroanilinium)2CuX4 (X = Cl, Br)

Successive structural phase transitions of (4-ClC₆H₄NH₃)₂CuCl₄, which occur in a very narrow temperature range were reinvestigated by Fourier transform nuclear quadrupole resonance (FT NQR) measurements. The phase transitions at 275.5 and 277.0 K were confirmed. The effect of the deuteration of the ammonium end on these transitions was studied. The³⁵Cl NQR frequencies of organic cation were observed to decrease by about 4 kHz and the phase transition temperatures to decrease by about 2 K by the deuteration, suggesting that the ?NH₃ ⁺ … Cl hydrogen bond is weakened by the deuteration. The magnetic phase transition temperature of 8.6 K showed no remarkable change within experimental error by the deuteration. It was found that the magnetically ordered state is broken by the radio-frequency magnetic field of about 15–35 Oe usually employed in pulsed NQR. However, in the deuterated compound (4-ClC₆H₄ND₃)₂CuCl₄, the ordered state was found to be stabler for the usual radiofrequency power. By combining with the NQR data of (4-ClC₆H₄NH₃)₂CuBr₄ and (3,5-Cl₂C₆H₃NH₃)₂CuCl₄, the possibility is discussed of tuning the interlayer interaction between the organic cation layer and the inorganic complex anion layer by the halogen substitution in the organic cation as well as by the halogen replacement in the inorganic complex anion.     

Cation mobility in the Cu6PS5X (X=Cl,Br, I) argyrodites

The electrical conductivity of Cu₆PS₅Cl shows purely Arrhenius behavior throughout the temperature range 170–450 K with no evidence of the 241 K thermodynamic phase transition previously reported. Cu₆PS₅Br exhibits two changes in activation energy. The first, at 251 K, apparently coincides with a previously determined thermodynamic transition. The second, at 321 K, is likely associated with a conduction transformation from ionic to electronic. The conductivity of Cu₆PS₅I is characterized by a cusp at a temperature of 194 K, far removed from a previously reported thermodynamic transition at 221 K. In addition, a broad and continuous change in activation energy appears to coincide with another previously reported phase transition at 270 K.     

NQR study of phase transitions in CH$\mathsf{_3}$HgX (X = Cl,Br, I)

The temperature dependence of halogen nuclear quadrupole resonance (NQR) in the series CH₃HgX (X = Cl, Br, I) is measured with special emphasis on the structural phase transitions at T _c = 162 K, 310 K, and 400 K, respectively. In the temperature dependences of NQR frequencies similarities are observed and discussed in relation with the structure and thermal vibrations on both sides of the phase transition. On the basis of known data a mechanism for the three analogous phase transitions is proposed. The chlorine spin-lattice relaxation behaviour in CH₃HgCl can be explained by a competition of fast thermal fluctuations of MMX molecules across the high temperature (h.t.) mirror plane and of infrequent transitions to the other equivalent fluctuation mode across the orthogonal h.t. mirror plane. Proton high temperature relaxation is probably dominated by the same slow motion, but at lower temperatures some other mechanism involving magnetic coupling prevails.Received: 23 June 2003, Published online: 15 October 2003PACS: 64.70.Kb Solid-solid transitions - 61.66.Fn Inorganic compounds - 76.60.Gv Quadrupole resonanceSupported in part by the Ministry of Education, Science and Sport, Republic of Slovenia     

NQR, NMR and Crystal Structure Studies of [C(NH2)3]2HgX4 (X = Br, I)

The crystal structure of [C(NH₂)₃]₂HgBr₄ has been determined at room temperature: monoclinic, space group C2/c, with a = 10.035(2), b = 11.164(2), c = 13.358(3) Å, β = 111.67(3)°, and Z = 4. The crystal consists of planar [C(NH₂)₃]⁺ and distorted tetrahedral [HgBr₄]^2? ions. The Hg atom is located on a two-fold axis such that two sets of inequivalent Br atoms exist in an [HgBr₄]^2? ion. In accordance with the crystal structure, two ⁸¹Br NQR lines widely separated in frequency were observed between 77 and ca. 380 K. [C(NH₂)₃]₂HgI₄ yielded four ¹²⁷I NQR lines ascribable to m = ±1/2 ? ±3/2 transitions, indicating that its crystal structure is different from the bromide complex. The ¹H NMR T ₁ measurements showed a single minimum for the bromide but two minima for the iodide. The analyses based on the C₃ reorientations of the planar [C(NH₂)₃]⁺ ions gave the activation energies of 29.8 kJ mol^?1 for the bromide, and 30.2 and 40.0 kJ mol^?1 for the iodide.     

Optical properties of the alkaline-earth fluorohalides matlockite-type structure SrFX (X=Cl, Br, I) compounds

The optical properties of the SrFX (X=Cl, Br, I) compound have been reported using the full potential linearized augmented plane wave (FP-LAPW) method as implemented in the WIEN2K code. We employed the generalized gradient approximation (GGA), which is based on exchange-correlation energy optimization to calculate the total energy. Also we have used the Engel-Vosko GGA formalism, which optimizes the corresponding potential for band structure calculations. Our calculations show that the valence band maximum (VBM) and conduction band minimum (CBM) are located at Γ resulting in a direct energy gap. We present calculations of the frequency-dependent complex dielectric function ε(ω) and its zero-frequency limit ε₁(0). We find that the value of ε₁(0) increases on decreasing the energy gap. The reflectivity spectra and absorption coefficient have been calculated and compared with the available experimental data.     

晶体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱研究

在强场耦合图像中,采用双自旋-轨道耦合(SO)参量模型建立了过渡族3d2(3d8)离子的三角对称下全组态光谱能级和电子顺磁共振(EPR)公式.与经典的晶体场理论(仅考虑中心金属离子的自旋-轨道耦合作用)相比较,该公式还包括了配体离子的自旋-轨道耦合作用的贡献,这一模型在应用于计算共价性较强的晶体光谱和电子顺磁共振谱可得到合理的结果.作为验证,用完全对角化方法研究了品体NiX2(X=Cl,Br,I)的光谱和电子顺磁共振谱,结果表明,理论与实验很好地符合.建立的全组态谱能级和电子顺磁共振公式为更精确地计算光谱和电子顺磁共振谱提供了一条可行方法.     

A CW-EPR and ESEEM spectroscopic study of the dithiadiazolyl radicals p-XC6F4CNSSN (X = CN, Br)

Two dithiadiazolyl radicals, p-NCC₆F₄CNSSN and p-BrC₆F₄CNSSN, have recently been found to be paramagnetic in the solid state. While the β-phase of the first one exhibits spontaneous magnetization below 36 K, the second one shows a paramagnetic character in the solid state. The spin density distribution in these radicals is examined through continuous-wave electron paramagnetic resonance and electron spin echo envelope modulation spectroscopies. Hyperfine correlation sublevel spectroscopy provides information about the interaction of the unpaired spin with F and N nuclei. A signal coming from the interaction with Br nucleus is also detected. The superhyperfme coupling constants of the unpaired electron with the magnetic nuclei are obtained and values of the corresponding spin densities, ?_s and ?_σ - ?_π, can be estimated in the isolated radicals. Spin density distribution has also been calculated in both molecules with density functional theory, being in excellent agreement with those determined from the spectra. The spin density is mainly concentrated in the dithiadiazolyl ring, but some spin density is observed on the fluorinated aromatic rings. They also provide a strong basis to understand the differences of the magnetic behavior of both molecules in terms of their respective packing in the solid state.     

Phonon softening in (C2H5)4NFeX4 (X=Cl,Br)

Temperature-dependent¹⁶⁹Tm Mössbauer measurements are reported for the ternary intermetallic compounds TmT₂Ge₂ (T=Fe, Cu). Based on comparison with results for their TmT₂Si₂ counterparts, it is verified that the T constituent has the more significant influence on the crystal field interaction at the rare-earth site.     

Electronic and magnetic properties of single-layer and double-layer VX_2(X=Cl,Br) under biaxial stress

First-principles calculations and Monte Carlo simulations reveal that single-layer and double-layer VX_2(X = Cl, Br)can be tuned from antiferromagnetic(AFM) semiconductors to ferromagnetic(FM) state when biaxial tensile stress is applied. Their ground states are all T phase. The biaxial tensile stress at the phase transition point of the double-layer VX_2 is larger than that of the single-layer VX_2. The direct band gaps can be also manipulated by biaxial tensile stress as they increases with increasing tensile stress to a critical point and then decreases. The Néel temperature(TN) of double-layer VX_2 are higher than that of single-layer. As the stress increases, the TNof all materials tend to increase. The magnetic moment increases with the increase of biaxial tensile stress, and which become insensitive to stress after the phase transition points.Our research provides a method to control the electronic and magnetic properties of VX_2 by stress, and the single-layer and double-layer VX_2 may have potential applications in nano spintronic devices.     

Halogen bond between hypervalent halogens YF3/YF5 (Y=Cl,Br, I) and H2X (X= O,S, Se)

ABSTRACT

The complexes of H₂X (X?=?O, S, Se) with hypervalent halogens YF₃ and YF₅ (Y?=?Cl, Br, I) have been studied. The σ-hole on the Y atom participates in a halogen bond with the lone pair on the chalcogen atom. In addition, some secondary interactions coexist with the halogen bond in most complexes. The interaction energy correlates with the nature of both X and Y atoms. In most cases, the complex is more stable for the heavier Y atom and the lighter X atom. Of course, there are some exceptions in H₂X···YF₃. YF₃ forms a more stable complex with H₂X than does YF₅. These complexes are dominated by electrostatic interaction and the halogen bond involving H₂S and H₂Se exhibits some covalent character.

Halogen bond plays an important role in chemical reactions and multivalent halogens can regulate chemical reactions by participating in a halogen bond. Thus we compare the effect of the chalcogen electron donor on the strength and nature of halogen bonding involving multivalent halogens.     

Nonreciprocal light birefringence in the R 3B7O13 X Boracites (R=Co, Cu, Ni; X=I, Br)

The field and angular dependences of nonreciprocal birefringence (NB), which is linear in magnetic field B and is due to magnetic-field-induced spatial dispersion, have been studied in the cubic (symmetry class T _d) paraelectric phase of the R ₃B₇O₁₃ X boracites (R=Co, Cu, Ni; X=I, Br) at a wavelength λ=633 nm. It is shown that the NB in crystals with different 3d and halogen ions exhibits the same anisotropy. The relation between the A and g parameters, A=2g, which determine the NB anisotropy, suggests that the microscopic mechanism of the NB is the manifestation of second-order magnetoelectric susceptibility at optical frequencies.     

Lattice and molecular dynamics in (C2H5)4NFeX4(X=Cl,Br)

We have measured the thermal dependence of thef factor and the line shift of the title compounds, in order to determine the (−2) and (+2) moments of the Fe frequency spectrum. The latter is approximated by a superposition of an acoustic-wave band and an intramolecular optical mode. Our results show that both frequency bands are well separated, owing to a relatively weak interaction between tetrahedral units. Optical frequencies thus determined are consistent with Raman data. Debye temperatures were obtained for the low-frequency vibrations of both crystals.     

High-pressure magnetic and structural properties of TiOX (X=Cl,Br)

We report high-pressure diffraction and magnetization measurements to demonstrate that the partial collapse of electronic gap at high-pressure insulator to metal transition reported in TiOCl (C. Kuntscher et al. Phys. Rev. B 74 184402 (2006).) corresponds to a Ti³⁺–Ti³⁺ dimerization at room temperature within the space group P2₁/m. The shortest Ti–Ti distance is comparable to that of the Ti metal, but a Peierls-like distortion prevents a metallic behaviour.     

Investigations of the optical and EPR spectra for (NiX6) (X=Cl, Br, I) clusters

In this paper, the formulae of optical spectral levels and electron paramagnetic resonance (EPR) spectra in trigonal symmetry of 3d⁸ ions are established on the basis of strong field mechanism and a two spin-coupling (SO) parameters model. Unlike the classical crystal-field approach which has only taken the SO coupling of the central metal ions into account, the contribution of the SO coupling of the ligand ions to the optical and EPR spectra has been included in these formulae. When the optical and EPR spectra of the strong covalent crystals are calculated, the reasonable results can be obtained if the two SO parameters model has been put into action. As an application, the optical and EPR spectra of the (NiX₆)⁴⁻ clusters in CsMgX₃:Ni²⁺ (X=Cl, Br, I) crystals have been studied by the complete diagonalization (of energy matrix) method (CDM). The calculated results agree well with experimental findings. From the investigations, a more valid method to calculate the optical and EPR spectra for 3d⁸ ions clusters is provided.