Two-photon absorption and energy band structure of orthorhombic Hg2Cl2 crystals

Dependence of two-photon absorption (TPA) rate on the state of polarization of a laser beam is investigated in the low-temperature orthorhombic modification of Hg₂Cl₂ crystals. Theoretical calculations of the dependence of TPA rate on the direction of polarization vector of the beam are performed for centrosymmetric points, Y, Z, T, R andS of the Brillouin zone. The domain structure of real crystals is taken into consideration and it is shown that periodicity of the polarization dependence may indicate whether TPA is due to transitions either at, Y, Z, T orR, S points. The polarization dependence of TPA cannot, however, distinguish between points inside these two groups. Comparison of theory with a low-temperature (T 8·5 K) experimental curve of polarization dependence is discussed. It is shown that the experiment can be explained in main features by a model of noninteracting oriented linear dipoles. Further, on the basis of TPA measurements, a simple energy band structure of Hg₂Cl₂ is proposed regarding Hg₂Cl₂ crystal as a linear chain of molecules.The authors express thanks to Dr. . Barta for supplying the Hg₂Cl₂ crystals, Dr. Z. Bryknar for critical comments and Dr. B. Velický for stimulating discussion. We thank also Dr. V. Kohlová for assistance during measurement.     

Improved gain on the Cl2(D′3 П g −A′3 П u ) transition at 258 nm by halogen donor mixing

The temporal development of the small-signal gain on the Cl₂(D–A) transition at 258 nm has been investigated by means of an amplified spontaneous emission (ASE) technique. For electron beam pumped He/Cl₂ mixtures, the gain appears only at the end of the pumping pulse, whereas for He/Cl₂/CCl₄ mixtures the temporal gain profile coincides with the fluorescence pulse, and the maximum gain coefficient increases by about a factor of two. The observed effects are due to the mixing of both halogen donors and can be explained by considering the quenching of theD-state by electrons.     

Submillimeter laser action of CW optically pumped CF2Cl2 (Fluorocarbon 12)

Eleven new CW far infrared (FIR) laser lines have been observed in the 600 m–1200 m range from the CF₂Cl₂ (Fluorocarbon 12) molecule optically pumped by a CO₂ laser. A 510^–4–10^–3 accuracy is achieved in the measurement of the FIR wavelengths.The frequency offset between the CO₂ pump center and the absorption line centers are measured using the transferred Lamb dip technique. Owing to a recent spectroscopic study of the CF₂ ³⁵Cl₂ molecule three lines may be assigned with great confidence as rotational transitions in thev ₆ vibrational band 923 cm^–1 of this main isotope.     

Raman spectroscopy of ionic liquids derived from 1‐n‐butyl‐3‐methylimidazolium chloride and niobium chloride or zinc chloride mixtures

Anionic species formed in mixtures of 1‐n‐butyl‐3‐methylimidazolium chloride (BMICl) with different amounts of niobium pentachloride (NbCl₅) or zinc dichloride (ZnCl₂) were investigated by Raman spectroscopy. In the BMICl and NbCl₅ ionic mixtures the presence of the anion NbCl₆⁻ was detected for all compositions (molar fraction, X) and a mixture of this anion and the neutral Nb₂Cl₁₀ in acid ones. Two different anions were observed for basic mixtures of BMICl and ZnCl₂: ZnCl₄²⁻(0 < X < 0.35) and Zn₂Cl₆²⁻(X > 0.3), whereas for acidic ones three species were detected: Zn₂Cl₆²⁻(X < 0.7), Zn₃Cl₈²⁻(X > 0.7) and Zn₄Cl₁₀²⁻(X > 0.7). It has also been observed that in both cases, the formation of larger anions causes a shift of the C H stretching modes to higher wavenumbers as the result of a decrease in the hydrogen bond between Cl and the hydrogens from the cation. Copyright © 2008 John Wiley & Sons, Ltd.     

A Pulsed-Periodic, Low-Pressure Volume Discharge in Chlorine and in a Xenon/Chlorine Mixture

The electrical and optical characteristics of a self-initiated, low-pressure, pulsed-periodic discharge in chlorine and in a xenon/chlorine mixture are investigated. A volume discharge not bounded by dielectric walls was triggered in a spherical anode–plane cathode system of electrodes on supply of a constant positive-polarity voltage to the anode. The discharge existed in the form of a unit domain. The spatial, spectral (in the range 150–350 nm), and time characteristics (voltage, current, and photocurrent of total radiation of plasma in the spectral range 200–700 nm) of the volume discharge are investigated. Optimization of the pressure and of the structure of the working medium is carried out to obtain the maximum brightness of UV–VUV radiation of the bands of the Cl₂(D–A), Cl₂ ^**, and XeCl(D, B–X) molecules. The results obtained are of interest for being used in a pulsed-periodic, excimer-halogen low-pressure lamp.     

Neutron scattering study of the two-dimensional spinS=1/2 square-lattice Heisenberg antiferromagnet Sr2CuO2Cl2

We have carried out a neutron scattering investigation of the static structure factorS(q _2D ) (q _2D is the in-plane wave vector) in the two-dimensional spinS=1/2 square-lattice Heisenberg antiferromagnet Sr₂CuO₂Cl₂. For the spin correlation length we find quantitative agreement with Monte Carlo results over a wide range of temperature. The combined Sr₂CuO₂Cl₂-Monte Carlo data, which cover the length scale from 1 to 200 lattice constants, are predicted without adjustable parameteres by renormalized classical theory for the quantum nonlinear sigma model. For the structure factor peakS(0), on the other hand, we findS(0) ² for the reduced temperature range 0.16<T/2 _s <0.36, whereas current theories predict that at low temperaturesS(0)T ^{2 2}. This discrepancy has important implications for the interpretation of many derivative quantities such as NMR relaxation rates. In the ordered phase, we have measured the temperature dependence of the out-of-plane spin-wave gap. Its low-temperature value of 5.0 meV corresponds to an XY anisotropyJ _XY /J=1.4×10^–4. From measurements of the sublattice mangetization we obtain =0.22±0.01 for the order parameter exponent. This may either reflect tricricality as in La₂CuO₄, or it may indicate finite-size two-dimensional XY behavior as suggested by Bramwell and Holdsworth. As in theS=1 system K₂NiF₄, the gap energy in Sr₂CuO₂Cl₂ scales linearly with the order parameter up to the Néel temperature. We also reanalyze static structure factor data for K₂NiF₄ using the exact low temperature result for the correlation length of Hasenfratz and Niedermayer and including the Ising anisotropy explicitly. Excellent agreement between experiment and theory is obtained for the correlation length, albeit with the spin-stiffness _s reduced by 20% from the spin-wave value. As in Sr₂CuO₂Cl₂ we find thatS(0) ² for the reduced temperature range 0.22<T/2 _s <0.47.     

Multiwave Low‐Pressure Excimer Radiator

The excitation conditions and characteristics of a longitudinal glow discharge in a short tube of small diameter in Kr/Cl₂ and Ar/Kr/Cl₂ mixtures are investigated. It is shown that this discharge is a multiwave radiation source on systems of the 199/222/258 and 175/199/222/258 nm bands. Optimization of the pressure and composition of working mixtures most applicable for obtaining the approximately equal intensity of the ArCl(B X), KrCl(D, B X), and Cl₂(DA) radiation bands is carried out in the discharge investigated. A multiwave UVVUV radiation source is of interest for use in photometry, microelectronics, photochemistry, and medicine.     

Competitive network modification in non-oxide chalcogenide glasses structural and motional properties of glasses in the system Li2S-P2S5-B2S3 studied by multinuclear NMR techniques

Non-oxide chalcogenide glasses based on more than one network former species have certain advantages for applications as solid electrolytes in batteries. To elucidate the influence of competitive glass-formation on the structural and motional properties of ionically conductive chalcogenide glasses, the system (Li₂S)_0.67[(B₂S₃)_1–y (P₂S₅) _y ]_0.33 has been characterized comprehensively by DSC, electrical conductivity and⁶Li,⁷Li,³¹P, and¹¹B solid state NMR techniques. The data obtained provide the first systematic characterization of the coformer effect in a chalcogenide glass system. Homogeneous glassy samples are formed fory=0.3 and 0.9y1.0, and microphase separated glasses for 0y0.2. The presence of a coformer leads to an increase in the electrical conductivity and a decrease of the activation energy, as compared to either binary system (Li₂S-B₂S₃ or Li₂S-P₂S₅), but only if homogeneous glasses are formed. The NMR data, in conjunction with systematic DSC and NMR studies of the binary systems (Li₂S)x(B₂S₃)_1–x (0.50x0.75) and (Li₂S) _x (P₂S₅)_1–x (0.50x0.70), lead to the following conclusions: 1)¹¹B MAS-NMR is well-suited to quantitate the amounts of three- and four coordinated boron atoms; in the binary glasses, the fraction of four-fold boron (N₄) increases with decreasing Li₂S/B₂S₃ ratio; in the ternary glasses N₄ increases with increasingy. 2)³¹P MAS-NMR spectra of the binary glasses discriminate between three different phosphorus microenvironments, assigned to sulfide-analogs of metaphosphate, pyrophosphate, and orthophosphate species, respectively. These results suggest the applicability of network modification models originally developed for oxide glasses. For the ternary glasses, the DSC and NMR data of glasses with low phosphorus contents are consistent with a phase separation model involving a Li-rich thioborate glass that contains all of the phosphorus component and a glass phase less rich in lithium containing the four-fold boron atoms. In addition to the structural studies, the⁷Li spin-spin relaxation times (T ₂) are used to characterize the mobility of the Li atoms. The activation energy of Li motion, determined from temperature dependentT ₂ measurements and analyzed by using BPP theory differs from that determined from conductivity measurements by a factor of 2–3, possibly reflecting the inapplicability of this theory to the lithium diffusion process.     

Clifford algebras and Hestenes spinors

This article reviews Hestenes' work on the Dirac theory, where his main achievement is a real formulation of the theory within thereal Clifford algebra Cl _1,3 M₂ (H). Hestenes invented first in 1966 hisideal spinors and later 1967/75 he recognized the importance of hisoperator spinors Cl _1,3 ⁺ M₂ (C).This article starts from the conventional Dirac equation as presented with matrices by Bjorken-Drell. Explicit mappings are given for a passage between Hestenes' operator spinors and Dirac's column spinors. Hestenes' operator spinors are seen to be multiples of even parts of real parts of Dirac spinors (real part in the decompositionC Cl _1,3 andnot inC M₄ (R)=M₄ (C)). It will become apparent that the standard matrix formulation contains superfluous parts, which ought to be cut out by Occam's razor.Fierz identities of bilinear covariants are known to be sufficient to study the non-null case but are seen to be insufficient for the null case ₀=0, ₀₀₁₂₃=0. The null case is thoroughly scrutinized for the first time with a new concept calledboomerang. This permits a new intrinsically geometric classification of spinors. This in turn reveals a new class of spinors which has not been discussed before. This class supplements the spinors of Dirac, Weyl, and Majorana; it describes neither the electron nor the neutron; it is awaiting a physical interpretation and a possible observation.Projection operators P_±, _± are resettled among their new relatives in End(Cl _1,3 ). Finally, a new mapping, calledtilt, is introduced to enable a transition from Cl _1,3 to the (graded) opposite algebra Cl _3,1 without resorting to complex numbers, that is, not using a replacement i.     

A remarkable difference in the deprotonation steps of the Friedel–Crafts acylation and alkylation reactions

Friedel–Crafts acylation and alkylation reactions were investigated using density functional theory calculations. The reaction systems studied were (benzene + acetyl chloride + Al₂Cl₆ (or AlCl₃)) and (benzene + 2‐chloropropane + Al₂Cl₆). In the acylation reaction, the acylium ion intermediate is reached either via a Me? C(Cl)?O? Al₂Cl₆ complex or via direct Cl transfer: Me? C(?O)Cl? Al₂Cl₆ → Me? C?O^?+? Al₂Cl. The ion adds to benzene electrophilically to form a Wheland intermediate containing a strong C? H? Cl hydrogen bond, which leads to deprotonation and the subsequent formation of acetophenone. The resulting H? Cl? Al₂Cl₆ fragment is subjected to a nucleophilic attack by the carbonyl oxygen of the acetophenone, and recovery of the Al₂Cl₆ bridge is unlikely. Attack of the Al₂Cl₆ moiety by Me? C(Cl)?O gives the complex Me? C(Cl)?O–AlCl₃, whose reactivity toward acylation is similar to that of the Me? C(Cl)?O–Al₂Cl₆ complex. In the alkylation reaction, deprotonation does not take place, but rather a [1,2] H‐shift from the Wheland intermediate. The resulting α‐protonated cumene undergoes deprotonation, with subsequent recovery of the Al₂Cl₆ bridge. In addition, the Al₂Cl₆‐catalyzed isomerization of the n‐propyl to the isopropyl cation was found to be a dyotropic shift. Copyright © 2009 John Wiley & Sons, Ltd.     

X-ray initiated molecular photochemistry of Cl-containing adsorbates on a Si(1 0 0) surface using synchrotron radiation

X-ray initiated molecular photochemistry for SiCl₄ and CCl₄ adsorbed on Si(1 0 0) at ∼90 K following Cl 2p core-level excitation is investigated by photon stimulated ion desorption and ion kinetic energy distribution measurements. The Cl excitation of solid SiCl₄ induces the significant enhancement (∼900%) of the Cl⁺ yield, while the Cl excitation of condensed CCl₄ leads to a moderate enhancement (∼500%) of the Cl⁺ yield. The enhancement of Cl⁺ yield at the specific core-excited states is strongly correlated to the ion escaped energy. Upon X-ray exposure for CCl₄ adsorbed on Si(1 0 0) (20-L exposure), the Cl⁺ yields at resonances decrease and new structures at higher photon energies are observed. Cl⁺ yields at these new resonances are significantly enhanced compared to those at other resonances. These changes are the results of desorption and surface reaction of the CCl₄-Si surface complex due to X-ray irradiation. We have demonstrated that state-specific enhancement of ion desorption can be successfully applied to characterize the reaction dynamics of adsorbates adsorbed on surfaces by X-ray irradiation.     

Zero magnetic field splitting and anomalies of intensities in the Zeeman spectra of La(Pr)Cl3-crystals

Optical absorption and Zeeman effect measurements on La(Pr)Cl₃ show a zero magnetic field splitting of the degenerate Pr³⁺ levels and . The site symmetry of the Pr³⁺ ions is lowered fromC _3h toC _s . The resultant splittings of the doublet levels are:I ³ H ₄:2|T _ak |=(0.12±0.05)cm^–1;a ³ P ₁:2|T _al |=(0.10±0.05)cm^–1.The intensities of the optical transitions induced by the deformation decrease with increasing magnetic field. All observations are described by a first order perturbation calculation using a low symmetric part of the crystal field and Zeeman energy as simultaneous perturbations on a Pr³⁺ ion in a crystal field with site symmetryC _3h .Project of the Sonderforschungsbereich Festkörperspektroskopie SFB65, Darmstadt—Frankfurt, supported by the Deutsche Forschungsgemeinschaft.     

Detection of chlorinated hydrocarbons via Laser-atomization/Laser-induced fluorescence

Chlorinated hydrocarbons (CHC), photodissociated at 193 nm, are detected with high sensitivity by observing the atomic chlorine fragment via laser-induced fluorescence (LIF). Photofragment emission spectra from CH₃Cl, CH₂Cl₂, CHCl₃, CCl₄, C₂HCl₃, and C₂Cl₄ demonstrate that photofragment fluorescence and chemiluminescence are negligible in the region 700–800 nm where the 3p ⁴4p ⁴ S ⁰ 3p ⁴4s ⁴ P fluorescence from atomic chlorine is detected. There is also negligible interference for photodissociation in Ar, N₂, and air bath gases. Total CHC can be readily detected in air flows at mixing fractions less than 20 ppb and averaging times less than 1 minute. Techniques for considerable improvement in this detection limit are discussed.Supported by the NSF     

Structural characterisation of [Cu2(bptd) (H2O) Cl4] and [Ni2(bptd)2(H2O)4] Cl4·3H2O; evidence of null intramolecular exchanges by EPR and magnetic measurements

Using the 2,5-bis(2-pyridyl)-1,3,4-thiadiazole (bptd), we recently prepared [Cu₂(bptd) (H₂O) Cl₄] and [Ni₂(bptd)₂ (H₂O)₄] Cl₄, 3H₂O in which the magnetic centres are connected through one diazine+one chloro and two diazine ligand bridges, respectively. These two compounds are the first examples that show null intramolecular magnetic interactions despite M-M distances close to 3.7 Å within perfectly planar edifices:Down to , [Cu₂(bptd)Cl₄(H₂O)] is paramagnetic while, below T_t, half of the Cu²⁺ions interact, leading to residual paramagnetism of one Cu²⁺/f.u. Magnetic susceptibility measurements, EPR and pulsed EPR study indicate the original intermolecular nature of AF exchanges.[Ni₂(bptd)₂(H₂O)₄]Cl₄·3H₂O susceptibility obeys a Curie-law involving pure paramagnetism. Moreover, its EPR spectrum can be interpreted on the basis of virtual S=1 monomers. Below 70 K, Zero Field Splitting (D∼275 G) due to dipolar interactions without magnetic exchanges could be responsible for the LT spectra splitting. For both compounds, the thia role is suggested as partially responsible for the null-in-plane magnetic exchanges.     

Magnetic susceptibility and specific heat of the spin-${\frac{1}{2}}$ Heisenberg model on the kagome lattice and experimental data on ZnCu3(OH)6Cl2

We compute the magnetic susceptibility and specific heat of the spin- Heisenberg model on the kagome lattice with high-temperature expansions and exact diagonalizations. We compare the results with the experimental data on ZnCu₃(OH)₆Cl₂ obtained by Helton et al. [Phys. Rev. Lett. 98, 107204 (2007)]. Down to k_BT/J≃0.2, our calculations reproduce accurately the experimental susceptibility, with an exchange interaction J≃190 K and a contribution of 3.7% of weakly interacting impurity spins. The comparison between our calculations of the specific heat and the experiments indicate that the low-temperature entropy (below ~20 K) is smaller in ZnCu₃(OH)₆Cl₂ than in the kagome Heisenberg model, a likely signature of other interactions in the system.     

Effect of halide ion concentration and irradiation dose dependent photostimulated luminescence investigation in the image screen phosphor CsBr1-xClx:Euy 2+

Photoluminescence(PL) characterization is carried out on CsBr_1-xCl_x:Eu_y²⁺ (x = 0.05, 0.1, 0.2, 0.3 y = 100 ppm, 200 ppm) crystals grown in vacuum with the Bridgman technique. PL studies show an increase in luminescence intensity with a decrease in bromide ion content. F(Br^–) and F(Cl^–) centers are formed due to -ray irradiation at room temperature. Photostimulated luminescence (PSL) emission is found to increase with an increase in irradiation dose from 7.5 Gy to 30 Gy at room temperature. From the results it is demonstrated that out of the different compositions studied, CsBr_0.9Cl_0.1:Eu²⁺ (200 ppm) phosphor has a linear PSL response with respect to irradiation dose.     

The ν4 and ν2 + ν5 high resolution infrared bands of FClO3 and FClO3

The high resolution infrared spectra of monoisotopic F³⁵Cl¹⁸O₃ and F³⁷Cl¹⁸O₃ have been studied in the region of the ν₄ fundamentals, centered at 1278.3 and 1263.3 cm⁻¹, respectively. Large perturbations are observed in both bands due to a Fermi type anharmonic resonance with the ν₂ + ν₅ combination bands, centered at 1270.7 cm⁻¹ in F³⁵Cl¹⁸O₃ and 1257.3 cm⁻¹ in F³⁷Cl¹⁸O₃. In particular, they affect the kl > 0 levels of the v₄ = 1 and v₂ = v₅ = 1 states which cross at kl ? 18 in F³⁵Cl¹⁸O₃ and kl ? 3 in F³⁷Cl¹⁸O₃, due to the opposite values of and . The Δl = Δk = ±2 and Δl = 0, Δk = ±3 essential resonances are also effective in the excited states of the dyad in F³⁵Cl¹⁸O₃, while in F³⁷Cl¹⁸O₃ only the Δl = Δk = ±2 one is active. In the spectrum of F³⁵Cl¹⁸O₃ 3423 transitions have been assigned, 10% of them belonging to ν₂ + ν₅. The rovibrational parameters and the interaction constants between the v₄ = 1 and v₂ = v₅ = 1 levels have been obtained. The depertubed band origins of ν₄ and ν₂ + ν₅ are 1277.310567(165) and 1271.753733(195) cm⁻¹, respectively, and the anharmonic resonance constant is 2.804416(153) cm⁻¹. For F³⁷Cl¹⁸O₃, 3022 transitions have been assigned, 38% belonging to the ν₂ + ν₅ combination band. The depertubed band origins are 1260.856338(123) and 1259.872338(134) cm⁻¹, for ν₄and ν₂ + ν₅ and the constant is 2.9350669(405) cm⁻¹. The equilibrium geometry of perchloryl fluoride, r_e (ClO) = 139.7(3) pm, r_e (ClF) = 161.0(5) pm, and α_e (OClO) = 115.7(4) degree, has been determined using the A_e and B_e equilibrium constants of the four symmetric isotopologues of perchloryl fluoride, F^35/37Cl¹⁶O₃ and F^35/37Cl¹⁸O₃.     

Surface analysis of Hg2Cl2

A surface composition of (110) face of Hg₂Cl₂ in high vacuum is studied for the room temperature. The impact of primary electrons with energy of 2·5 keV causes a decomposition of the surface layer which is described in detail.The single crystals of Hg₂Cl₂ used in this work were prepared by Dr. Barta in Institute of Solid State Physics of Czechosl. Acad. Sci., Prague.