FTMW spectroscopy of jet-cooled 9-cyanoanthracene

Rotational spectrum of jet-cooled 9-cyanoanthracene has been observed in the 4-8 GHz region with a Fourier-transform microwave spectrometer. The present observation of 25 low-J transitions with J^′′?11 has confirmed the previous results on the rotational constants of the ground state determined by rotational coherence spectroscopy [J. Phys. Chem. A. 105 (2001) 1131] and provided the values with significantly improved precision. An accurate set of hyperfine splitting constants is also reported for the ¹⁴N nuclear quadrupole coupling. The electric dipole moment was determined from Stark effect measurements on several split components: μ_b(=μ)=4.406(7) D.     

Spectroscopic Properties of LiNbO<Subscript>3</Subscript>:Tm<Superscript>3+</Superscript> Crystal in the 1650–1970 nm Wavelength Range

Taking into account the Stark structure of optical spectrum of the impurity ion, the theoretical study of spectroscopic properties of LiNbO₃:Tm³⁺ crystal in the wavelength range of 1650–1970 nm was carried out. The wave functions of the Stark sublevels of both ground ³H₆ and the first excited ³F₄ manifolds of the Tm³⁺ ion were constructed in the LSJM-representation, the line strengths induced by indirect electric-dipole transitions were calculated, and the main spectroscopic characteristics of emission and absorption spectra of impurity ion were determined.     

Spectroscopic and magnetic susceptibility analyses of the FJ and D4 energy levels of Tb(4f) in TbAlO3

Detailed analyses of spectroscopic and temperature-dependent magnetic susceptibility data are reported for the crystal-field split energy levels of the ⁷F_J and ⁵D₄ of Tb³⁺ in stoichiometric single crystals of ortho-aluminate TbAlO₃. The spectroscopic data include absorption spectra obtained between 2940 and 480 nm from 8 to 300 K. High resolution fluorescence spectra are reported, representing transitions from ⁵D₄ to ⁷F_6,5,4, at a sample temperature of 85 K. Using crystal-field modeling techniques recently adapted for low symmetry systems, we have assigned all 58 experimental Stark levels within the ⁷F_J and ⁵D₄ manifolds, with a fitting standard deviation of 4.5 cm⁻¹ (3.8 cm⁻¹ rms error). As a further test, the theoretical Stark levels and calculated wavefunctions were used to determine the temperature dependence of the magnetic susceptibility along the c-axis of the TbAlO₃ crystal. Good agreement is obtained between the calculated susceptibility and temperature-dependent magnetic data reported earlier, including a prediction of a 0.2 cm⁻¹ splitting of the ground-state quasi-doublet. The susceptibility calculation also confirms the predicted ordering of states within the ⁷F₆ multiplet manifold.     

Spectra, energy levels, and symmetry assignments for Stark components of Eu(4f) in gadolinium gallium garnet (Gd3Ga5O12)

Absorption and fluorescence spectra observed between 450 and 750 nm at 85 K and room temperature (300 K) are reported for Eu³⁺(4f⁶) in single-crystal Czochralski-grown garnet, Gd₃Ga₅O₁₂ (GGG). The spectra represent transitions between the ^2S+1L_J multiplets of the 4f⁶ electronic configuration of Eu³⁺ split by the crystal field of the garnet. In absorption, Eu³⁺ transitions are observed from the ground state, ⁷F₀, and the first excited multiplet, ⁷F₁, to multiplet manifolds ⁵D₀, ⁵D₁, and ⁵D₂. The Stark splitting of the ⁷F_J multiplets (J=0-6) was determined by analyzing the fluorescence transitions from ⁵D₀, ⁵D₁, and ⁵D₂ to ⁷F_J. The Eu³⁺ ions replace Gd³⁺ ions in sites of D₂ symmetry in the lattice during crystal growth. Associated with each multiplet manifold are 2J+1 non-degenerate Stark levels characterized by one of four possible irreducible representations (irreps) assigned by an algorithm based on the selection rules for electric-dipole (ED) and magnetic-dipole (MD) transitions between Stark levels in D₂ symmetry. The quasi-doublet in ⁵D₁ was characterized by an analysis of the magneto-optical spectra obtained from the transitions observed between ⁵D₁ and ⁷F₁. A parameterized Hamiltonian defined to operate within the entire 4f⁶ electronic configuration of Eu³⁺ was used to model the experimental Stark levels and their irreps. The crystal-field parameters were determined through use of a Monte-Carlo method in which nine independent crystal-field parameters, were given random starting values and optimized using standard least-squares fitting between calculated and experimental levels. The final fitting standard deviation between 57 calculated-to-experimental Stark levels is 5.9 cm⁻¹. The choice of coordinate system, in which the nine are real and the crystal-field z-axis is parallel to the [0 0 1] crystal axis and perpendicular to the xy plane, is identical to the choice we used previously in analyzing the spectra of Er³⁺ and Ho³⁺ garnets.     

Influence of J-mixing on the phenomenological interpretation of the Eu3+ ion spectroscopic properties

Two sets of B^k_q crystal field parameters and Bγ_kq intensity parameters have been calculated from the transition occuring between the Stark levels of Eu³⁺ in KY₃F₁₀. One of the calculations includes the J-mixing; the other not. The influence of the J-mixing on the intensities of the “forbidden” transition ⁵D₀ → ⁷F₀ and on the hypersensitive transitions are analysed.     

Observation of the dynamic Stark effect at microwave frequencies in a molecular beam maser

Multiplet splitting of the main doublet of the ¹⁴NH₃, J = K = 1 inversion line has been observed in a molecular beam maser spectrometer when a strong microwave radiation field is introduced into the maser cavity. This phenomenon is attributed to the dynamic Stark effect at microwave frequencies.     

Theoretical Study of the Dynamic Stark Effect on Dissociation of CsI

The influence of the dynamic Stark effect on the dissociation of CsI is theoretically studied by the time-dependent wave-packet method. After a pump pulse induces a dissociating wave packet that propagates through both the ionic channel X0⁺(Cs ⁺(¹ S ₀)?+?I ⁺(¹ S ₀)) and the covalent channel A0⁺(Cs(² S _1/2)?+?I(² P _3/2)), a Stark pulse is applied to control the diabatic-dissociation dynamics. The first-order non-resonant non-perturbative dynamic Stark effect gives control over the break up, the dissociation probabilities in the two channels being controlled by the delay between the pump and Stark pulses. With a 720-fs delay, the dissociation probability through channel A is greatly enhanced.     

Level-Crossing-Experimente zur Untersuchung der Hyperfeinstruktur des 5d 2 D 5/2-Terms im Indium I-Spektrum

The resonance fluorescence of the transition 5d ² D _5/2?5p ² P _3/2 (λ=3256Å) in the In I-spectrum was observed as a function of an external magnetic field. From the level crossing signals the following values of the hyperfine constantsA andB of the 5d ² D _5/2-state were deduced: ¦A¦=148(8) Mc/sec·g _J/1.2 and ¦B/A¦≦0.3. The widths of the signals yielded the mean lifetimet=7.1 (6)·10^?9 sec · 1.2/g _J . From the shifts of the signals caused by a constant electric field parallel to the magnetic field the value of the Stark parameter ¦β¦=0.19(4) Mc/sec/(kV/cm)² ·g _J /1.2 and the sign of the ratioA/β<0 were determined. Calculations with Coulomb wave functions show that the Stark shifts of the electric field are mainly due to admixtures of the 6p ² P _3/2-state.     

Measurement of the dipole moment of CF3CN

The Stark effect was observed for K = 0 and K = 1, J = 1 → 2 transitions in CF₃CN. Measurements were made in a Stark modulated microwave spectrometer. The dipole moment obtained was μ = 1.262 ± 0.010 D. An analysis of the effects of electric field inhomogeneities on the observed Stark shifts for K = 0 and K = 1 states is included. Appropriate corrections are given for measuring linear Stark effects in a standard waveguide cell calibrated using a molecule with second-order Stark effect.     

Comparative study of the VMI model expressions for the fitting of the rotational spectrum of a single intrinsic wave function

Skyrme's method is used to introduce a correlation coefficient which tells us which of the VMI model expressions should be considered better in the calculation of the projected energies E_J when one uses a single intrinsic wave function for a set of good J-states. As an application of the correlation coefficient, we have shown that out of several VMI model expressions for the energy which have the same overlap with the Hamiltonian, the one having minimum dispersion should be considered to be the best choice. A remark is passed that the Holmberg-Lipas model can also be derived using Bohr and Mottelson's conditions. Numerical calculations are carried out for the nuclei ²⁸Si and ³⁶Ar using Ripka's Hartree-Fock wave functions to compare Holmberg-Lipas model with the one in which one directly expands the energy E_J in powers of J(J + 1), where J is the total angular momentum.     

Submillimeter-wave spectroscopy of HCO in the excited vibrational states

The pure rotational transitions of HCO⁺ in excited vibrational states located below 5000 cm⁻¹ over the ground state have been investigated with a high-sensitivity frequency/magnetic field double modulation submillimeter-wave spectrometer in the frequency range of 280-810 GHz. The ions were generated in an extended negative glow discharge through a gas mixture of a few millitorrs of H₂ and CO and 12 mTorr of Ar buffer gas. Throughout the experiments, the cell was maintained at liquid nitrogen temperature. In the present study, we have determined accurate molecular constants for the excited vibrational states. Our analysis suggests that there may be a higher order Coriolis interaction between the (0 3 1) and (1 2 0) states. In previous investigations, the Stark effect caused by the electric field present in the discharge plasma was cited as a reason for non-observations of low-J lines in the (02²0) and for the systematic shifts observed for low-J lines in the (01¹0), (02²0), (03¹0), and (04²0) states of HCO⁺ as well as DCO⁺. In the present investigation, some low-J lines in the (02²0) and (04²0) states have been observed in emission. Furthermore, J = 8-7, J = 9-8 lines in (03^1e1) were detected in emission. This finding indicates that missing low-J lines for the Δ sublevel obtained in the past is not due to the Stark effect but due to small population differences in those levels.     

Molecular transient effects in K-band spectroscopy

The time dependence of microwave transient absorption and emission was measured forJ=2←1 of the OCS molecule under on- and off-resonant conditions by the technique of Stark switching. The results are analyzed with the theory of a coherent electromagnetic wave interacting with a two-level quantum system through the electric dipole interaction to obtain the pressure dependence of the relaxation timesT ₂ and in consequence the pressure broadening parameterC _w=26.7±0.9 (μs·mTorr)^?1 has been obtained.     

Der Einfluß eines elektrischen Feldes auf Level-Crossings des 6d 2 D 3/2-Zustands im TlI-Spektrum

The influence of an electric field on the energy levels of the 6d²D_3/2-state in the Tl I-spectrum was studied by measuring the shifts of level crossing signals relative to their magnetic field positions. The following values of the magnetic hyperfine constantA and the Stark parameterβ were deduced: ¦A¦=42(2) Mc/sec · g_J/0.8, ¦β¦=0.12(1) Mc/sec/(kV/cm)² · g_J/0.8 and A/β>0. Assuming that the main part of the energy shifts are caused by admixtures of the 7p²P-states the sign of the Stark parameterβ and —from the measured ratio A/β>0 —the sign of theA-factor should be negative. For electric field strength E?30 kV/cm the energy shifts of the 6d²D_3/2state are considerably greater than the hyperfine structure splitting. Therefore the case of decoupled hyperfine structure is considered.     

Analyses of 4f11 Energy Levels and Transition Intensities Between Stark Levels of Er3+ in Y3Al5O12

ABSTRACT

Absorption and fluorescence spectra obtained at temperatures as low as 4 K were investigated between 200 and 1550 nm on samples containing approximately 1.2 at. wt. % Er in Y₃Al₅O₁₂ (YAG). Within this wavelength range 125 experimental energy (Stark) levels were analyzed, representing data that span 29 ^2S+1 L _J multiplet manifolds of Er³⁺(4f¹¹) in D₂ sites up to an energy of 44,000 cm^?1. Agreement between calculated and observed Stark levels was achieved with an r.m.s. deviation of 11.2 cm^?1. These transitions originate from the ground-state Stark level in the ⁴I_15/2 manifold to J + 1/2 Stark levels associated with each of the 28 excited-state manifolds. A total of 88 ground-state absorption transition line strengths were measured for 19 ^2S+1 L _J multiplet manifolds between 280 and 1550 nm. For line strength measurements, the Er³⁺ ion is assumed to be distributed homogeneously throughout the D₂ cation sites of Y³⁺ in the lattice. The line strengths were analyzed with a weighted (E _i  ? C _i )/E _i , with an r.m.s. error of 0.25. Use of a “vector crystal field” parametrization resolves ambiguities in the transition intensity parameters and allows for the definition of polarization-resolved Judd-Ofelt parameters, which may have wide-ranging applicability for future Judd-Ofelt-type intensity calculations.     

Resonanzstreuung von Licht in magnetischen und elektrischen Feldern zur Untersuchung der Hyperfeinstruktur des 7d 2 D 3/2-Terms im Thallium I-Spektrum

Observing the resonance fluorescence of the transition 7d ² D _3/2-6p ² P _1/2 (λ=2379 Å) in the Tl I-spectrum the level crossing technique with combined electric and magnetic fields was used to investigate the hyperfine structure and the Stark effect of the 7d ² D _3/2-state. For electric field strengthsE?25 kV/cm the Stark shifts are considerably greater than the hyperfine splitting. Therefore the crossing signals for the case of decoupled hyperfine structure could be detected. The following values of the magnetic hyperfine constantA and the Stark parameterβ were deduced: ¦A¦=55(1) Mc/sec·g _J /0.8, ¦β¦=0.20(4) Mc/sec/(kV/cm)²·g _J /0.8 andA/β>0. The widths of the signals yielded the mean lifetimeτ=2.7(5)·10^?8 sec· 0.8/g _J . Sign and values ofA andβ are discussed.     

The Stark and Zeeman effects in methyl silane

The Stark and Zeeman effects in methyl silane in the ground vibronic state have been studied in detail using the molecular-beam electric-resonance method. For a symmetric rotor without internal rotation, the rotational dependence of the effective dipole moment for matrix elements diagonal in J has been shown by Watson, Takami, and Oka to have the form μ_Q = μ₀ + μ_JJ(J + 1) + μ_KK². It is shown here that, to this order, a complete characterization of the Stark effect requires only one more parameter, namely, the effective anisotropy (α_| - α_⊥)_eff in the polarizability. From Stark measurements alone, the true anisotropy cannot be separated from the additional dipole distortion constant shown by Aliev and Mikhaylov to enter dipole matrix elements off-diagonal in J. By studying nine different transitions (J, K, m_J) → (J, K, m_J ± 1) in CH₃²⁸SiH₃, values were obtained for the four Stark parameters: μ₀ = 0.7345600(33) D, μ_J = 8.83(35) μD, μ_K = ?32.82(37) μD, and (α_| - α_⊥)_eff = 1.99(16) × 10^?24 cm³. These errors reflect only the internal consistency in the data; the absolute error in μ₀ is 32 μD. The modification of the Stark effect by internal rotation is discussed; it is shown that the only significant effect here is to modify the interpretation of μ₀. The change in μ₀ upon isotopic substitution of ³⁰Si for ²⁸Si was determined: $\text{μ}{}_0\text{(}{}^{30}\text{Si) - μ}{}_0\text{(}{}^{28}\text{Si) = 67.0(2.0) μD}$. A study of molecular magnetic effects in CH₃²⁸SiH₃ has yielded the two molecular g factors, g_⊥ = ?0.036391(21) nm and g_| = ?0.10667(13) nm, as well as the anisotropy in the susceptibility $\text{(χ}{}_{\mathrm{|}}\text{- χ}{}_{\mathrm{\perp }}\text{) = ?44.9(2.3) × 10}{}^{\mathrm{?30}}\text{J}\text{T}{}^2$. The molecular quadrupole moment has been calculated.     

Jump diffusion coefficient of different cations intercalated into amorphous WO3

This work shows how the combination of quasi-equilibrium (chronopotentiometry) and kinetical measurements (electrochemical impedance) is able to extract ionic mobility values like the jump diffusion coefficient D_J. Results are presented on the jump diffusion coefficient variation with composition of several cations (Li⁺, Na⁺, and K⁺) intercalated into electron beam evaporation-prepared a-WO₃ thin films. D_J exhibits higher values for the smallest ion (Li⁺), and decreases as the ion size enlarges. In all cases D_J shows lower values for high intercalation levels. It is noted that the type of cation rather influences transport mechanisms than equilibrium properties (insertion thermodynamics). The energy barrier of ion hopping is analyzed in light of available microscopic diffusion models and theoretical simulations.     

Probabilities of rovibronic transitions in the I 1Π g − , J 1Δ g − →C 1Π ± u systems of bands of the deuterium molecule

Probabilities of spontaneous rovibronic transitions I ¹Π _g ^? , v′ J′, J ¹Δ _g ^? , v′, J′→C ¹Π _u ^± , v″, J″ of the D₂ molecule (for vibrational and rotational quantum numbers v′=v″=0–3 and J′=1–9, J″=J′±1) have been obtained for the first time. They were determined using (1) the previously proposed nonadiabatic model, which takes into account the electron-rotational interaction of the upper levels; (2) the coefficients of expansion of wave functions of perturbed states in the Born-Oppenheimer basis, which were found from the experimental data on rovibronic terms; and (3) semiempirical b initio data on electronic transition dipole moments of the 3dπ¹Π_g→2pπ¹Π_u and 3dπδ¹Δ_g→2pπ¹Π_u transitions. The dependences of the transition probabilities on J′ for the same bands of both hydrogen isotopomers H₂ and D₂ were found to be identical. They represent monotone functions for R and P branches and functions with a maximum (minimum) for Q branches. The ratios of transition probabilities of different isotopomers for different branches of the same systems of bands and for the same branches of different systems of bands were found to be correlated. The semiempirical values obtained in the paper agree with the experimental values within the limits of the errors of their determination. The nonempirical values of transition probabilities agree with the experiment considerably worse.     

Laser-Stark spectrum of NH3 with the CO laser: Determination of the ground state dipole moment

Results from analysis of sub-Doppler laser-Stark spectra of ¹⁴NH₃ obtained using a CO laser and an intracavity Stark cell are given. Over 1500 Lamb dips have been identified, associated with about 200 NH₃ lines. The data are analyzed to determine relative frequencies between the laser lines and the NH₃ lines. In favorable cases this can be done with an accuracy of 5–10 MHz. Analyses of a portion of the data yield the expression for the ground state dipole moment in Debye, μ^H(J, K) = 1.47182(30) + 1.654(190) × 10^?4J(J + 1) ? 3.095(300) × 10^?4K².     

Nuclear effects in the hadroproduction and photoproduction ofJ/ψ

Hadroprduction ofJ/ψ in π^? nucleus collisions is studied in the context of the colour singlet model using nuclear structure functions from three different models of the EMC effect. We conclude that it is possible to understand the data on the large transverse momentum (p _T ) and small Feynmanx (x _F ) of theJ/ψ in terms of the nuclear dependence of structure functions alone. We further show that these data can be used to distinguish between different models of the EMC effect, and that a study of distributions in various kinematic variables in photoproduction ofJ/ψ should be able to very effectively supplement the information obtained from hadroproduction experiments.