Electric field induced anomalies in frequency shift and collisional perturbations in the 5snd D2 Rydberg series of strontium in a heatpipe setup with ionization detection

We have examined the effect of weak DC electric field (2-20 V/cm) complimented by foreign gas collisions on the bound J = 2 even-parity 5snd ¹D₂ Rydberg states of neutral strontium. We use resonant two-photon transverse excitation, employing a narrow bandwidth tunable dye laser and an atomic jet in a heatpipe setup with ionization detection. In this paper we report certain anomalies in the observed spectra covering principal quantum number range n = 27-42 indicating a frequency shift reversal with nearly quadratic dependence on the field strength above an anti-resonance region. Furthermore, we have observed the emergence of highly localized doubly-excited 4d² states, including a remarkably broad perturber with large angular momentum, uncovering orbital contraction effect. This non-Rydberg excitation, which intrudes upon the two-photon spectrum with large energy overlap is due to single-photon excitations from the 5s5p ¹P₁ resonance level following molecular dissociation of the Sr₂ dimers suitably governed by binary atomic collisions. Our study which involves laser excitation complimented by electric field and collisions using inexpensive home-made setup opens up the possibilities for a new class of experiments, with considerable simplicity in the choice of excitation schemes for both Rydberg and non-Rydberg transitions, to reach states lying at high energies which cannot otherwise be accessed from the ground state due to parity and selection rules, while allowing one to probe localization properties of atomic wave functions.     

Two-color three-photon excitation studies of thallium Rydberg states

We present new data on the even-parity Rydberg states of atomic thallium using two-step three-photon laser excitation technique in conjunction with a thermionic diode ion detector. Atoms are excited from the 6p ²P_1/2 ground state to the 7p ²P_1/2 intermediate state via two-photon excitation and subsequently promoted to the high lying ns ² S_1/2 and nd ²D_3/2 Rydberg states. The first ionization potential of thallium is determined as 49,266.66(1) cm^-1 using data for the ns ² S_1/2 (25 ≤ n ≤ 54) and nd ²D_3/2 (24 ≤ n ≤ 65) Rydberg series. This value is believed to be more accurate because the contribution due to the hyperfine structure splitting of the 7p ²P_1/2 state (0.07185 cm^-1) is much smaller as compared to that of the 6p ²P_1/2 ground state (0.711 cm^-1).     

Multi-step laser excitation of the highly excited states of zinc

We report experimental data on the highly excited states of zinc in the energy range 74,625-75,740 cm⁻¹ using two-step laser excitation scheme in conjunction with a thermionic diode ion detector. The 4s4p ³P₁ inter-combination level at 32501.399 cm⁻¹ was populated using a frequency doubled dye laser. The 4s5s ³S₁ level at 53672.28 cm⁻¹ gets populated from the ASE (amplified spontaneous emission) of the second step dye laser. The Rydberg series 4snp ³P₂ (12 ? n ? 60), 4snp ¹P₁ (16 ? n ? 30) and parity forbidden transitions 4sns ³S₁ (19 ? n ? 44) have been observed. A two parameter fit to excitation energies of the observed series yields the binding energy of the 4s5s ³S₁ level as 22097.03 ± 0.03 cm⁻¹ and consequently, the first ionization potential of zinc is determined as 75769.31 ± 0.05 cm⁻¹, that is in excellent agreement with the earlier work.     

Impact broadening and shifts for 6sns 1S0 and 6snd 1D2 series of barium

Impact broadening and shifts of Ba transitions to parity forbidden Rydberg states have been measured using two-photon laser spectroscopy techniques. Broadening and shift rates for the 6sns ¹S₀ (10 < n < 19) and 6snd ¹D₂ (8 < n < 26) levels due to thermal collisional interactions with Xe, Kr and Ar as perturber gases are plotted. Perturbations due to configuration interactions are discussed.     

Investigation of the 6p 2(3 P 0)n p Rydberg series of bismuth by multiphoton excitation

Rydberg states of the odd-parity series 6p ²(³ p ₀)n p of BiI are excited by a three-photon process. A two-photon dissociation of Bi₂ into excited atomic states followed by a one-photon absorption leads to highly excited atomic Rydberg states up ton = 32. States of the even-parity Rydberg series 6p ²(³ p ₀)nsJ=1/2,ndJ=3/2 andndJ=5/2 are also observed. In order to avoid the background caused by ionization of the bismuth molecules we performed a two-color excitation with pulsed dye lasers. With this experiment the 6p ²(³ p ₀)npJ=3/2 Rydberg series could be resolved up ton=75. The increasing quantum defect of this series is due to a perturbing state close to the first ionization limit. By a MQDT analysis we obtain the energy of the perturbing state and a value of 58,761.68±0.1 cm^?1 for the first ionization limit of atomic bismuth.     

The pure rotational spectrum of Difluoroiodomethane, CHF2I

The pure rotational spectrum of CHF₂I has been recorded for the first time, in a supersonic expansion in the region 1.7-17 GHz, and at room-temperature in the region 302-318 GHz. The observed transitions span the values of J^″ from 0 up to 67. Precise rotational and centrifugal distortion constants have been determined. Furthermore, the complete iodine nuclear electric quadrupole coupling tensor, in the inertial and principal axes, has been determined. Quantum chemical calculations have been performed to aid with the analysis. Iodine quadrupole mediated perturbations have resulted in the following observations: (i) several transitions having enhanced intensities and (ii) the observation of several forbidden, ΔJ=±2, transitions. Comparisons in electronic structure are made between the series of molecules CH_3-nF_nX; and X = Cl, Br, I.     

一价铝离子能级结构的多通道量子亏损理论分析

利用多通道量子亏损理论(MQDT)对一价铝离子(AIII)的各受干扰序列:3sns ¹S₀,3snp ³P_0,1,2^O,¹P₁^O,3snd ¹D₂和3snf³F_2,3,4^O的能级结构进行理论分析。结果表明:前两个序列所受到的干扰较弱,后三个序列则受到了来自干扰态3p4s ¹P₁^O,3p^{2 1}D₂和3p3d³F_2,3,4^O的强烈干扰,而3snf ¹F₃^O序列则受到来自电离限上方干扰态的影响。利用获得的MQDT参数推算出3p3d ¹F₃^O干扰态位于电离限上方5613cm^-1处,这一结果与其他作者的预言相符合。 关键词：     

Spin-orbit coupling of the NaK 3Π and 3Π states: Determination of the coupling constant and observation of quantum interference effects

We have studied the mutually perturbing 3³Π_Ω=0(v = 32, J = 19) ∼ 3¹Π_Ω=1(v = 6, J = 19) levels of NaK that are coupled together by the spin-orbit interaction. We note that this coupling is nominally forbidden by the ΔΩ = 0 selection rule for spin-orbit perturbations. However 3³Π levels labeled by different values of Ω are mixed by rotational coupling; i.e. the 3³Π_Ω levels are best described by a coupling scheme intermediate between Hund’s cases (a) and (b). Thus the 3¹Π_Ω=1 level couples to the 3³Π_Ω=0 level via the small admixture of 3³Π_Ω=1 character in the latter. The 3³Π_Ω=0(v = 32, J = 19) ∼ 3¹Π_Ω=1(v = 6, J = 19) f symmetry pair is of particular interest since it appears to be very close to a 50-50 mixture of triplet and singlet character, and the splitting between these levels provides a direct measure of the 3³Π ∼ 3¹Π spin-orbit coupling constant. On the other hand, excitation spectra of the 3³Π_Ω=0(v = 32, J = 19) ∼ 3¹Π_Ω=1(v = 6, J = 19) e symmetry pair through the mixed “window” levels 1(b)³Π_Ω=0(v = 17, J = 18, 20) ∼ 2(A)¹Σ⁺(v = 18, J = 18, 20) display dramatic quantum interference effects associated with “singlet” and “triplet” excitation channels. Almost complete cancellation for populating one or the other of the two upper states is observed for excitation from the predominantly triplet members of the window level pairs.     

Pressure dependence of spectral positions and widths of emission lines related to DJ→FJ electronic transitions in Sm ions doped into SrFCl single crystal

The pressure dependence of the peak positions and widths of the fluorescence lines corresponding to the ⁵D_J→⁷F_J electronic transitions in Sm²⁺-doped SrFCl crystals was measured at room temperature (RT) with a diamond anvil cell (DAC) and a high-pressure gas system, using silicone oil and gaseous helium as the pressure-transmitting medium, respectively. At RT and ambient pressure the electronic transitions ⁵D₀→⁷F_J (J= 0, 1, 2, 3) and ⁵D₁→⁷F_J (J=0, 1, 2) in Sm²⁺ ions yielded rather sharp spectral lines peaked at 14490, 14206, 13685, 13012 cm⁻¹ and 15823, 15533, 15012 cm⁻¹, respectively. At pressures up to 45 kbar in the DAC all these peaks shifted linearly to lower energies at the rates −2.36, −2.10, −2.43, −2.22 cm⁻¹/kbar and −2.35, −2.33, −2.47 cm⁻¹/kbar. Under purely hydrostatic gas pressure up to 7 kbar at RT the initial (normal pressure) widths of the ⁵D₀→⁷F₀, ⁵D₀→⁷F₁ and ⁵D₁→⁷F₀ lines having a Lorentzian profile (with corrected FWHM values of 1.55, 5.71 and 1.97 cm⁻¹) decreased linearly with increasing pressure at the rates −0.009(2), −0.077(3) and −0.034(2) cm⁻¹/kbar, respectively. Possible mechanisms of the observed pressure effects are discussed. For further studies of linewidth variations with the pressure, gaseous helium as a best possible high-pressure medium is strongly recommended.     

Three-photon resonance enhanced excitation spectrum of atomic thallium

We present first measurements on the resonance enhanced three-photon excitation in thallium, using a Nd:YAG laser pumped dye laser in conjunction with a thermionic diode ion detector. The even-parity 6s²ns²S_1/2 (15 ? n ? 31) and nd ²D_5/2 (13 ? n ? 42) Rydberg states have been observed. The measured level energies reveal a dynamic shift from the photoabsorption values, which is decreasing with increasing n, while the asymmetry in the line profile is observed to be increasing with increasing n. In addition, an autoionising level (sp²⁴P_3/2) adjacent to the ionization threshold has been observed and quantitatively analyzed using the Fano’s photoionization cross-section relation for an isolated autoionising resonance.     

Upconversion luminescence in Yb/Tb-codoped monodisperse NaYF4 nanocrystals

Upconversion (UC) luminescence in monodisperse NaYF₄:Yb³⁺/Tb³⁺ nanocrystals was observed under diode laser excitation of 970 nm, which were synthesized by a hydrothermal method. UC emissions at 380, 413, 436 nm and at 488, 542, 584, 620 nm arise from transitions ⁵D₃(⁵G₆) → ⁷F_J(J = 6, 5, 4) and ⁵D₄ → ⁷F_J(J = 6, 5, 4, 3) of Tb³⁺ ions, respectively. UC mechanisms are proposed based on spectral, kinetic, decay time measurements, and pump power dependence analyses. Blue, green and red emissions originate from the same long-lived (milliseconds) upper ⁵D₄ state, which promises the potential applications of these monodisperse Yb³⁺/Tb³⁺-codoped NaYF₄ nanocrystals in the field of photonics, lasers and biomedicine.     

Infrared spectroscopic studies of the rare gas atom perturbed S1(0) rovibron band of solid parahydrogen

We report high resolution infrared absorption studies of rare gas (Rg) atom doped solid parahydrogen in the hydrogen S₁(0) region around 4486 cm⁻¹. At low Rg atom concentrations (∼0.1%), satellite transitions appear in the S₁(0) region due to rovibrational excitation of parahydrogen molecules with one nearest-neighbor Rg atom. The Ne satellite feature differs qualitatively from the Ar, Kr, and Xe satellite features for reasons described within. The frequency of the S₁(0) satellite features linearly shift to lower energy as the polarizability of the Rg atom increases while the absorption coefficients increase with the square of the Rg atom polarizability. Rotational calculations are performed for H₂ with a nearest-neighbor Rg atom assuming a rigid hexagonal close-packed lattice structure. The calculated fine structure of the S₁(0) satellite features agree qualitatively with lifting of the 2J+1 degeneracy of the v = 1, J = 2 upper state caused by the anisotropy in the Rg-H₂ intermolecular potential. The discrepancy between the calculated and measured Rg atom S₁(0) satellite features may signal partial delocalization of the J = 2 roton onto neighboring parahydrogen molecules.     

Rotational spectra of gauche perfluoro-n-butane, C4F10; perfluoro-iso-butane, (CF3)3CF; and tris(trifluoromethyl)methane, (CF3)3CH

The microwave spectra of the gauche conformer of perfluoro-n-butane, n-C₄F₁₀, of perfluoro-iso-butane, (CF₃)₃CF, and of tris(trifluoromethyl)methane, (CF₃)₃CH, have been observed and assigned. The rotational and centrifugal distortion constants for gauche n-C₄F₁₀ are: A = 1058.11750(7) MHz, B = 617.6832(1) MHz, C = 552.18794(1) MHz, Δ_J = 0.0257(5) kHz, δ_J = 0.0052(3) kHz. A C-C-C-C dihedral angle, ω, of ∼55° has been determined. These values agree well with those obtained from a coupled cluster (CCSD/cc-PVTZ) calculation. The rotational and centrifugal distortion constants for iso-C₄F₁₀ and iso-C₄HF₉ are: B_o = 816.4519(4) MHz, D_J = 0.023(2) kHz, and B_o = 903.6985(25) MHz, D_J = 0.043(4) kHz, respectively. The dipole moment of iso-C₄F₁₀ and iso-C₄HF₉ have been measured and found to be 0.0338(8) and 1.69(9) D, respectively.     

Nuclear hyperfine structure in the XΣ state of ZrC

Electronic band systems of zirconium monocarbide, ZrC, in the 16 000-19 000 cm⁻¹ region have been observed following the reaction of laser-ablated Zr atoms with methane under supersonic free-jet conditions. Rotational analyses of high-resolution spectra have shown that the ground state of ZrC is a ³Σ state, with r₀=1.8066 Å and an unexpectedly small spin-spin parameter, λ=0.5139 cm⁻¹. The spectra are dense because of the five naturally occurring isotopes of Zr. Four of these, with mass numbers 90, 92, 94, and 96, have I=0, but the fifth, ⁹¹Zr, present in 11.22% abundance, has I=5/2. Lines of ⁹¹ZrC can be assigned in some of the strongest bands, and are found to display sizeable hyperfine splittings, with widths of up to 0.2 cm⁻¹. Analysis shows that the largest hyperfine effects are in the ground state, where b=−0.03133±0.00015 cm⁻¹ and c=−0.00123±0.00037 cm⁻¹ (3σ error limits). The large Fermi contact parameter, b, indicates that an unpaired Zr 5sσ electron is present, which, taken together with the small value of λ, means that the ground state must be a ³Σ⁺ state, from the electron configuration (Zr 5sσ)¹ (C 2pσ)¹. Internal hyperfine perturbations occur between the F₁ and F₃ electron spin components of the ground state in the range N=2-4, producing extra lines in some of the branches; the perturbations are of the type ΔN=0, ΔJ=±2, and are a second-order effect arising because the F₁ (J=N+1) and F₃ (J=N−1) spin components both interact with the F₂ (J=N) component through ΔN=0, ΔJ=±1 matrix elements of the Fermi contact operator. Second-order perturbations of this type can only occur in states that are very close to case (b) coupling.     

The study of the radiative lifetimes of 3pndF3 and 3pndD3 of Si I

The energy levels and lifetimes of 3pnd¹F₃ (n = 3-15) and 3pnd³D₃ (n = 3-18) of neutral silicon are calculated and predicted by means of the multichannel quantum defect theory (MQDT). In addition, this paper corrects the assignment mistakes of 3pnd¹F₃, 3pnd³F₃ for n > 8, and predicts many positions and lifetime values of the energy state which are not obtained in theory and experiment up to now, and analyzes the perturbation images between the channels.     

D3→FJ emission of Tb doped sol–gel silica

Amorphous silica samples doped with 0.1 and 1 mol% of terbium (Tb) were synthesized by the sol–gel method. In addition to the green light associated with ⁵D₄→⁷F_J transitions of Tb³⁺, the sample containing 0.1 mol% also emitted blue light as a result of ⁵D₃→⁷F_J transitions during photoluminescence (PL) measurements. As a result of concentration quenching this blue emission was not observed for the samples doped with the higher concentration (1 mol%). However the blue ⁵D₃ →⁷F_J emission was observed in the 1 mol% doped samples during cathodoluminescence (CL) measurements. Since a rough calculation indicated that the excitation rate in the CL system where the blue emission is observed may be similar to a laser PL system under conditions where the blue emission is not observed, the difference is attributed to the nature of the excitation sources. It is suggested that during the CL excitation incident electrons can reduce non-luminescent Tb⁴⁺ ions in the silica, substituting for Si⁴⁺ ions, to the excited (Tb³⁺)? state and that these are responsible for the blue emission, which does not occur during PL excitation.     

Luminescence and crystal field analysis of Eu in Eu[Co(CN)6]·4H2O

The vibrational spectra of Eu[Co(CN)₆]·4H₂O and luminescence spectra of Eu³⁺ in this compound, using 355 nm excitation at temperatures down to 10 K, have been assigned. A clear distinction is made between the n=5 and 4 members of the Ln[M(CN)₆]·nH₂O series from the vibrational spectra. The electronic spectra show prominent vibronic structures, particularly for the ⁵D₀→⁷F₂ sideband. A resonance occurs between the transitions ⁵D₀→⁷F₁(III) and ⁵D₀→⁷F₀+ν(Eu−N). A crystal field analysis of the derived energy data set is presented for Eu³⁺ in eight coordination geometry.     

Dependence of photoluminescent properties of cubic Y2O3:Tb nanocrystals on particle size and temperature

Temperature-dependent spectral properties in the cubic Y₂O₃:Tb³⁺ nanocrystals (NCs, 10-70 nm) under 488 nm excitation were studied and compared to that in the bulk. In NCs, emission lines assigned to the ⁵D₄-⁷F_J (J=1-6) transitions of Tb³⁺ ions and a broad band originated from oxygen defects were observed. As a function of temperature, two intensity maximums of the ⁵D₄-Σ⁷F_J transitions appeared in the NCs, at ∼250 and ∼500 K, while in the bulk only one maximum appeared at ∼250 K. The relative intensity of the maximum at ∼500 K to that at ∼250 K increased with decreasing particle size. The intensity maximum of the band emissions that came from the oxygen defects appeared in the range of 500-600 K. The appearance of intensity maximum as a function of temperature was attributed to the rivalry between thermal quenching process and phonon-assisted excitation. The appearance of two maxima in the NCs was attributed to the luminescence contributed by different Tb³⁺ centers, the internal and the surface. The emission for the surface Eu³⁺ centers has higher quenching temperature in contrast to that for the internal centers.     

Synthesis and luminescence properties of red-emitting phosphors NaY0.87Eu0.13(WO4)1.2(MoO4)0.8

A series of NaY_1−yEu_y(WO₄)_2−x(MoO₄)_x (x=0−2 and y=0.06−0.15) phosphors have been prepared by a combustion route. X-ray powder diffraction, photoluminescence excitation and emission spectra were used to characterize the resulting samples. The excitation spectra of these phosphors show the strongest absorption at about 396 nm, which matches well with the commercially available n-UV-emitting GaN-based LED chip. Their emission spectra show an intense red emission at 616 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. As the Mo content increases, the intensity of the ⁵D₀→⁷F₂ emission of Eu³⁺ activated at wavelength of 396 nm increases and reaches a maximum when the relative ratio of Mo/W is 2:3. The intense red-emission of the tungstomolybdate phosphors at near-UV excitation suggests that the material is a potential candidate for white light emitting diode (WLEDs).     

Synthesis, microstructure and photoluminescence of Eu/Tb activated Y2SiO5 nanophosphors by new silicate sources

Y_2−xTb_xSiO₅ and Y_2−xEu_xSiO₅ nanophosphors with seven different kinds of silicate sources were synthesized by sol-gel method. The structures have been investigated to be composed of nanometer-size grains of 30-60 nm through X-ray diffraction (XRD) and scanning electron microscopy (SEM) was used to compare the different morphology of patterns from seven different silicon sources. The photoluminescence of Y_2−xTb_xSiO₅ was investigated as a function of silicate sources and the results revealed that these nanometer materials showed the characteristic emission ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) of Tb ions. The characteristic emission ⁵D₀ → ⁷F_J (J = 1, 2, 4) of Eu ions was also found in the materials of Y_2−xEu_xSiO₅.