Spectroscopic and structural proprieties of LiAr and LiAr<Subscript>2</Subscript> molecules

We determined and tried to understand the spectroscopic and structural properties of small LiAr and LiAr₂ molecules within a simple model considering LiAr as a result of interaction between a valence electron and a LiAr⁺ molecular ion. Potential energy curves, spectroscopic constants, and vibrational levels corresponding to the Li(2s, 2p, 3s, and 3p)+Ar dissociation are reported for the LiAr molecule. The depth of the potential well for the X ²Σ⁺ ground state is found to be 50 cm⁻¹ (the corresponding experimental value is (42.5±1.2) cm⁻1 [1]). R _e is determined to be 9.36 a.u. (the experimental value is 9.24 a.u.). For the first excited state A, R _e = 4.97 a.u. and D _e = 993cm ⁻¹ (the corresponding experimental values are 4.68 a.u. and (925−40) cm⁻¹, respectively [1]). The spacing between the vibrational levels for the ground and first excited states is in very good agreement with the experiment. For the ground state, the difference between our results and the data of the most recent experiment is about 1 cm⁻¹. The model has been extended to study the LiAr₂ molecule in two forms (linear and triangular). We have determined the potential energy surfaces of the states dissociating to Li(2s, 2p)+Ar₂ and thus found the triangular form to be more stable as compared to the linear one. We have also calculated the transition energy between the ground state and first excited states of this molecule. The emission spectrum of the Li(2s)+Ar₂→Li(2p)+Ar₂ transition in both forms redshifts as compared to the Li(2s)→Li(2p) atomic transition.     

Optical characterization of Cr3+ centers in LiNbO3

Low-temperature luminescence spectra of stoichiometric Cr:LiNbO₃, congruent Cr:LiNbO₃ and congruent Cr,Mg:LiNbO₃ were studied. Dominant low-field and minor high-crystal-field optical centers are the Cr³⁺ impurity ions that preferentially occupy Li⁺ sites (Cr_Li) in the Cr:LiNbO₃ crystals. Low-field centers related to Cr³⁺ substitution of Nb⁵⁺ (Cr_Nb) occur in addition to Cr_Li in co-doped Cr,Mg:LiNbO₃ samples. Application of high hydrostatic pressure leads to the transformation of dominant Cr³⁺ centers from low- to high-field type due to strong pressure-induced blue shift of the ⁴ T ₂ state, resulting in its crossing with the ² E state of Cr³⁺. This level-crossing effect was observed for the dominant Cr³⁺ _Li and Cr³⁺ _Nb centers at pressures that correlate well with estimations based on the ⁴ T ₂-² Eenergy gap (230 cm^-1 and 1160 cm^-1) and on the rate of their pressure-induced change (14.35 and 11.4 cm^-1/kbar, respectively). We also studied inhomogeneous broadeningof the ² E?⁴ A ₂transitions at ambient pressure for the minor high-field “defect” Cr³⁺ _Li centers in congruent LiNbO₃. A fine structure in the spectral response of these centers was observed. The obtained results are discussed on the basis of a microscopic hierarchic model for perturbed Cr³⁺ ions in the LiNbO₃ lattice. Received: 25 June 2001 / Published online: 2 November 2001     

Three-body decay of a rubidium Bose–Einstein condensate

We have measured the three-body decay of a Bose–Einstein condensate of rubidium (⁸⁷Rb) atoms prepared in the doubly polarized ground state F=m _F =2. Our data are taken for a peak atomic density in the condensate varying between 2×10¹⁴ cm^-3 at initial time and 7×10¹³ cm^-3, 16 s later. Taking into account the influence of the uncondensed atoms on the decay of the condensate, we deduce a rate constant for condensed atoms L=1.8 (±0.5) ×10^-29 cm⁶ s^-1. For these densities we did not find a significant contribution of two-body processes such as spin dipole relaxation. Received: 24 November 1998 / Revised version: 26 June 1999 / Published online: 8 September 1999     

Inner-shell excited quartet states in Li-like O<Superscript>5+</Superscript> and Ne<Superscript>7+</Superscript> ions

First laser spectroscopic measurements of the 6s5d³D₁-6s6p¹P₁ and 6s5d³D₂-6s6p¹P₁ transitions in several isotopes of atomic barium have been performed. The hyperfine structure of these transitions was optically resolved and isotope shifts for even and odd isotopes were determined. The isotope shifts show a deviation from their expected behavior for odd isotopes in an analysis based on King-plots. This observation puts atomic structure calculations at test because available theories do not predict this. A profound understanding of the wavefunctions for heavy alkaline earth systems like barium (Ba) and radium (Ra) is essential for a theoretical evaluation of their sensitivity to fundamental symmetry breaking effects such as they could be observed, e.g., through permanent electric dipole moments. Further the absolute frequency of the 6s^{2 1}S₀-6s6p³P₁ intercombination line in ¹³⁸Ba was determined to be 12 636.6232(1) cm^-1.     

Multi-wavelength excimer ultraviolet sources from a mixture of krypton and iodine in a dielectric barrier discharge

New ultraviolet (UV) sources (excimer lamps) have been demonstrated using mixtures of krypton and iodine in a high-pressure dielectric barrier discharge to provide intense multi-wavelength radiation at λ=183 nm (atomic iodine line, ⁴ P _5/2?² P _3/2), 191 nm (KrI^*, B _1/2?X _1/2), 206 nm (atomic iodine line, ² P _3/2?² P _1/2), and 342 nm (I^* ₂, D _1/2?X _1/2). The characteristics of the optical emission spectra of the atomic species and the excited dimers (excimers) formed for different total gas pressures and in the presence of a buffer gas have been investigated. The highest intensity, at 183 nm, is obtained at pressures up to 1 bar while the overall emission spectra can be controlled by adjusting the total pressure. The results show that these strong multi-wavelength lamps offer an interesting alternative to conventional UV sources. Received: 1 March 2000 / Revised version: 5 April 2000 / Published online: 30 June 2000     

Nuclear moments and charge radii of107–111in determined by laser spectroscopy

Collinear fast beam laser spectroscopy has been used to measure the hyperfine structure and isotope shift in the atomic 5s ² 5p ² P _3/2-5s ² 6s ² S _1/2 transition (λ=451 nm) of^107–111In. Secondary beams of neutron deficient indium isotopes were prepared at the GSI on-line mass separator following fusion evaporation reactions. Magnetic dipole moments and electric quadrupole moments have been determined. The isotope shifts are discussed in terms of the change of the mean square nuclear charge radii and compared with the droplet model predictions and the deformation values calculated from the quadrupole moments.     

Theoretical study of the electronic states and transition dipole moments of the LiK molecule

The adiabatic potential energy, the spectroscopic constants and the transition dipole moments of the lowest electronic states of the LiK⁺ molecule, dissociating into Li(2s, 2p, 3s, 3p, 3d, 4s, and 4p) + K⁺ and Li⁺ + K(4s, 4p, 5s, 3d, 5p, 4d, and 6s), have been investigated. We have used an ab initio approach involving a non-empirical pseudopotential for the Li (1s²) and K (1s²2s²2p⁶3s²3p⁶) cores and core valence correlation correction. A very good agreement has been obtained for the ground state for the spectroscopic constants with the available theoretical works. The transition dipole moment from X²Σ, 2²Σ, 3²Σ, and 4²Σ states to higher excited states have been determined. Numerous avoided crossing between electronic states of ²Σ and ²Π symmetries, have been localised and analysed. Their existences are related to the charge transfer process between the two ionic systems Li⁺K and LiK⁺.     

Cavity-enhanced absorption spectroscopy with a rapidly swept diode laser

Cavity-enhanced absorption spectroscopy is explained in terms of the transmission function of a rapidly swept interferometer, and the integrated transmission is shown to be proportional to the cavity ringdown time. The technique is demonstrated on the b¹Σ_g ⁺-X³Σ_g ^-  (1,0) band in molecular oxygen at 687 nm using a tunable diode laser and a relative-ly high-Q optical cavity (finesse ≈4000). A detection limit of 3×10^-8 cm^-1 s^1/2 is achieved for a 0.8 cm^-1 scanning range. Received: 24 June 2002 / Revised version: 5 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: peverall@physchem.ox.ac.uk     

Effect of stresses on the OH libration bands in proton-exchanged LiNbO3 optical waveguides

i -H_xLi_1-xNbO₃ phases generated on x-cut LiNbO₃ the new anisotropic libration mode at 890–940 cm^-1 is observed in addition to the known isotropic mode at 960–970 cm^-1, whereas the same phases on z-cut exhibit only latter isotropic libration mode. The observed phenomena are explained as a result of anisotropic stresses generated in the x-cut waveguides, whereas the stresses in the structures on z-cut are isotropic. The OH-bond librations are clearly anisotropic in the α, κ₁, and κ₂ phases generated on both z- and x-cuts, which indicates a fundamental difference of the local symmetry of the proton’s position in the β_i phases compared to the α, κ₁, and κ₂ H_xLi_1-xNbO₃ phases. Received: 4 May 1998/Revised version: 26 June 1998     

Solution‐Based Phototransformation of C60 Nanorods: Towards Improved Electronic Devices

A modified liquid–liquid interface precipitation synthesis of C₆₀ nanorods, effects and opportunities following an in situ photochemical transformation in the liquid state, and an electronic characterization using a field‐effect transistor (FET) geometry are reported. The nanorods feature a high aspect ratio of ≈10³ and a notably small average diameter of 172 nm. Interestingly, it is found that a decreased nanorod diameter appears to correlate with distinctly improved electronic properties, and an average electron mobility of 0.30 cm² V^?1 s^?1, as measured in a FET geometry, is reported for as‐grown nanorods, with the peak value being an impressive 1.0 cm² V^?1 s^?1. A photoexposure using green laser light (λ = 532 nm) is demonstrated to result in the formation of a polymer‐C₆₀ shell encapsulating a monomer‐C₆₀ bulk; such photo‐transformed nanorods exhibit an electron mobility of 4.7 × 10^?3 cm² V^?1 s^?1. It is notable that the utilized FET geometry only probes the polymer‐C₆₀ nanorod surface shell, and that the monomer‐C₆₀ bulk is anticipated to exhibit a higher mobility. Importantly, photoexposed nanorods can be conveniently processed as a stabile dispersion in common hydrophobic solvents, and this finding is attributed to the insoluble character of the polymer‐C₆₀ shell.     

Theoretical determination of the potassium far-wing photoabsorption spectra

This theoretical work reports full quantum-mechanical analysis of the potassium far-wing photoabsorption spectra. The accuracy of the adopted K₂ potential-energy curves and transition dipole moments is established by computing the vibration-rotation levels and the radiative lifetimes of the excited molecular states and by determining the variation law with temperature of the diffusion coefficient of atomic K(4p) in a ground potassium gas. The pressure-broadening calculations revealed that the photoabsorption spectra have, in the temperature range 850-3000 K, a satellite structure characterized by the presence of three peaks around 718.7 nm in the blue wings and 1048.1 and 1100.8 nm in the red wings. This theoretical work could in particular point out the occurrence in the blue wing of a satellite originating from the bound-free B←X transitions near 731.5 nm. All these results agree quite well with the experimentally measured values.     

An ab initio calculation of the rotational-vibrational energies in the electronic ground state of NH2

We have calculated ab initio the three-dimensional potential-energy surface of the NH₂ molecule at 145 nuclear geometries spanning energy ranges of about 18 000 cm^-1 for the NH stretch and 12 000 cm^-1 for the bend. The ab initio configuration-interaction calculations were done using the multireference MRD-CI method. The calculated equilibrium configuration has NH bond length r _e = 1·0207 Å and bond angle α = 103·1°. The rotational-vibrational energies for ¹⁴NH₂, ¹⁴NHD and ¹⁴ND₂ were calculated variationally using the Morse-oscillator rigid-bender internal-dynamics Hamiltonian. For ¹⁴NH₂ we calculate that υ₁ = 3267 (3219) cm^-1, υ₂ = 1462 (1497) cm^-1 and υ₃ = 3283 (3301) cm^-1, where experimental values are given in parentheses.     

Cu+ emission in Li2BPO5 material for thermoluminescence dosimetry

In this study, Li₂BPO₅ doped with Cu and that co-doped with Mg are synthesized by the wet chemical technique and exposed to γ rays of ⁶⁰Co to determine their thermoluminescence (TL) properties. The X-ray diffraction technique shows the crystalline nature of the prepared material. The photoluminescence (PL) emission spectra of Li₂BPO₅:Cu phosphor show the strong prominent peak at 368 nm in the violet region of the visible spectrum due to the transition of 3d⁹4s¹ ? 3d¹⁰ of monovalent copper ion. The PL emission of Li₂BPO₅:Cu is enhanced by the addition of Mg. The TL glow curves of γ-irradiated Li₂BPO₅:Cu sample show one glow peak at 143°C, indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak of Li₂BPO₅:Cu are calculated using the glow curve shape (Chen's) method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. A linear TL response is observed in Li₂BPO₅:Cu in a long span of exposures. The sensitivity of Li₂BPO₅:Cu sample is observed to be 7.8 times that of (TLD-100) LiF:Mg, Ti.     

Capillary discharge soft X-ray laslng in Ne-like Ar pumped by long current pulses

A capillary discharge soft X-ray laser operating at 46.9 nm on the transition 3p-3s (J = 0-1) of the Ne-like Ar has been realized by exciting the active medium with a long half-cycle duration current pulse of 140 ns. The current is produced by discharging a 10 nF water dielectric capacitor, initially charged to voltages lower than 200 kV by a six stage Marx generator, through a 15-cm long capillary channels. The laser amplification has been obtained by properly adjusting all the other experimental parameters. Utilizing a 3-mm in diameter Al₂O₃ capillary channel initially filled with 0.3 torr of Ar pressure, a laser beam, which has a 4-mrad divergence and a time duration of 1.3 ns, is characterized by a gain of 0.6±0.1 cm^-1. The stability of the plasma compression followed by the laser emission is verified. Received 13 December 2001     

The beryllium atom and beryllium positive ion in strong magnetic fields

The ground and a few excited states of the beryllium atom in external uniform magnetic fields are calculated by means of our 2D mesh Hartree-Fock method for field strengths ranging from zero up to 2.35×10⁹ T. With changing field strength the ground state of the Be atom undergoes three transitions involving four different electronic configurations which belong to three groups with different spin projections S _z = 0, - 1, - 2. For weak fields the ground state configuration arises from the 1s ²2s ², S _z = 0 configuration. With increasing field strength the ground state evolves into the two S _z = - 1 configurations 1s ²2s2p _-1 and 1s ²2p _-13d _-2, followed by the fully spin polarised S _z = - 2 configuration 1s2p _-13d _-24f _-3. The latter configuration forms the ground state of the beryllium atom in the high field regime γ > 4.567. The analogous calculations for the Be ⁺ ion provide the sequence of the three following ground state configurations: 1s^22s and 1s ²2p _-1 (S _z = - 1/2) and 1s2p _-13d _-2 (S _z = - 3/2). Received 2 October 2000 and Received in final form 8 January 2001     

V:YAG – a new passive Q-switch for diode-pumped solid-state lasers

gsa =3.0×10^-18 cm² and σ_esa=1.4×10^-19 cm² at 1064 nm, and σ_gsa=7.2×10^-18 cm² and σ_esa=7.4×10^-19 cm² at 1342 nm. Q-switched operation was demonstrated at 1064 nm and 1342 nm from a Nd:YVO₄ microchip laser, producing pulses as short as 9.3 ns at 1342 nm with peak powers of 350 W. Received: 17 March 1998/Revised version: 8 June 1998     

Solvent Effect on Absorption and Fluorescence Spectra of Three Biologically Active Carboxamides (C<Subscript>1</Subscript>, C<Subscript>2</Subscript> and C<Subscript>3</Subscript>). Estimation of Ground and Excited State Dipole Moment from Solvatochromic Method Using Solvent Polarity Parameters

The absorption and fluorescence spectra of three Carboxamides namely (E)-2-(4-Chlorobenzylideneamino)-N-(2-chlorophenyl)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₁), (E)-N-(3-Chlorophenyl)-2-(3, 4-dimethoxybenzylideneamino)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₂) and (E)-N-(3-Chlorophenyl)-2-(3, 4, 5-trimethoxybenzylideneamino)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₃) have been recorded at room temperature in solvents of different polarities using dielectric constant (ε) and refractive index (n). Experimental ground (μ_g) and excited (μ_e) state dipole moments are estimated by means of solvatochromic shift method and also the excited dipole moments are estimated in combination with ground state dipole moments. It was estimated that dipole moments of the excited state were higher than those of the ground state of all three molecules. Further, the changes in dipole moment (Dm \Delta \mu ) were calculated both from solvatochromic shift method and on the basis of microscopic empirical solvent polarity parameter (E_T^N E_T^N ) and the values are compared.     

Off-axis continuous-wave cavity-enhanced absorption spectroscopy of narrow-band and broadband absorbers using red diode lasers

We present an application of continuous-wave (cw) cavity-enhanced absorption spectroscopy (CEAS) with off-axis alignment geometry of the cavity and with time integration of the cavity output intensity for detection of narrow-band and broadband absorbers using single-mode red diode lasers at λ=687.1 nm and λ=662 nm, respectively. Off-axis cw CEAS was applied to kinetic studies of the nitrate radical using a broadband absorption line at λ=662 nm. A rate constant for the reaction between the nitrate radical and E-but-2-eneof (3.78±0.17)×10^-13 cm³ molecule^-1 s^-1 was measured using a discharge-flow system. A nitrate-radical noise-equivalent (1σ≡ root-mean-square variation of the signal) detection sensitivity of 5.5×10⁹ molecule cm^-3 was achieved in a flow tube with a diameter of 4 cm and for a mirror reflectivity of ∼99.9% and a lock-in amplifier time constant of 3 s. In this case, a noise-equivalent fractional absorption per one optical pass of 1.6×10^-6 was demonstrated at a detection bandwidth of 1 Hz. A wavelength-modulation technique (modulation frequency of 10 kHz) in conjunction with off-axis cw CEAS has also been used for recording 1f- and 2f-harmonic spectra of the ^RR(15) absorption of the b¹Σ_g ⁺-X³Σ_g ^- (1,0) band of molecular oxygen at =14553.947 cm^-1. Noise-equivalent fractional absorptions per one optical pass of 1.35×10^-5, 6.9×10^-7 and 1.9×10^-6 were obtained for direct detection of the time-integrated cavity output intensity, 1f- and 2f-harmonic detection, respectively, with a mirror reflectivity of ∼99.8%, a cavity length of 0.22 m and a detection bandwidth of 1 Hz. Received: 24 June 2002 / Revised version: 12 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: vlk@physchem.ox.ac.uk     

Re-dispersible Li<Superscript>+</Superscript> and Eu<Superscript>3+</Superscript> co-doped CdS nanoparticles: Luminescence studies

Re-dispersible CdS, 5 at.% Eu³⁺-doped CdS, 2 at.% Li⁺ and 5 at.% Eu³⁺ co-doped CdS nanoparticles in organic solvent are prepared by urea hydrolysis in ethylene glycol medium at a low temperature of 170°C. CdS nanoparticles have spherical shape with a diameter of ∼80 nm. The asymmetric ratio (A ₂₁) of the integrated intensities of the electrical dipole transition to the magnetic dipole transition for 5 at.% Eu³⁺-doped CdS is found to be 3.8 and this ratio is significantly decreased for 2 at.% Li⁺ and 5 at.% Eu³⁺ co-doped CdS (A ₂₁ = 2.6). It establishes that the symmetry environment of Eu³⁺ ion is more favored by Li-doping. Extra peak at 550 nm (green emission) could be seen for 2 and 5 at.% Eu³⁺ co-doped CdS. Also, the significant energy transfer from host CdS to Eu³⁺ is found for 5 at.% Eu³⁺-doped CdS compared to that for 2 at.% Li⁺ and 5 at.% Eu³⁺ co-doped CdS.      

Superlinear photovoltaic currents in proton-exchanged LiNbO<Subscript>3</Subscript> waveguides

Photovoltaic currents along the c axis have been measured in α-phase LiNbO₃ proton-exchanged waveguides at several visible wavelengths for a guided-beam configuration. The light-intensity dependence is superlinear and all experimental curves are very well fitted by computer simulations using a two-centre model, with Fe²⁺/Fe³⁺ as primary and Nb_Li ⁴⁺/Nb_Li ⁵⁺ as secondary photovoltaic centres. The superlinear behaviour arises from a much higher effective photovoltaic length of Nb_Li ⁴⁺ (small polaron) compared with that of Fe²⁺. In β₁-phase guides, the photocurrents are much smaller than in α-phase guides and apparently do not show superlinear behaviour. Received: 22 October 2002 / Revised version: 6 January 2003 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +34-91/3978-579, E-mail: m.carrascosa@uam.es