Investigation of lutetium rydberg states by laser multistep resonance ionization spectroscopy

Laser multistep excitation and electric-field ionization spectroscopy have been used to investigate experimentally highly excited states (HES) of lutetium in the vicinity of the first ionization limit. The investigation includes the measurement of energy levels (ionic signal vs last transition frequency) and radiation lifetime (ionic signal vs ionizing electric-field pulse delay) of the states investigated. Even Rydberg states of 4f ¹⁴ 6s ² nd have been observed with two-step laser excitation. The maximum experimental error is 0.3 cm^?1 for the energy and 20% for the radiation lifetime measurements. This is the very first time that results for the lifetimes as well as for a large part of the energy values have been obtained. Our present experimental results compare well with previously calculated values obtained by relativistic perturbation theory using the zero-order model approximation, and with the available experimental values.     

Fine structure and transition probabilities of the 2p 5 nl bound excited states of Ne atom

We present a semi-empirical calculational procedure for thep ⁵ nl bound excited states of rare gas atoms based on the use of an LS-dependent orbital for an excitednl electron outside a frozen Hartree-Fockp ⁵ core. The spin-orbit interaction is accounted for approximately using a localized Hartree potential. The contribution from the long-range core polarization is estimated by using a parametrized potential. A model potential is also introduced to represent partially the short-range multi-electron interactions for thep ⁵ np levels. The energy levels are calculated by diagonalizing the Hamiltonian matrix following anLS →jl transformation. The calculated fine structure of the Nep ⁵ ns,p ⁵ np,p ⁵ nd, andp ⁵ nf ¦ (jl)KJ〉 levels are in close agreement with the observed level splittings. The transition probabilities are also in agreement with earlier theoretical and experimental results.     

The Rydberg states of trans-butadiene from generalized valence bond and configuration interaction calculations

Self-consistent ab initio generalized valence bond (GVB) and configuration interaction (Cl) calculations are presented for the Rydberg states of trans-1,3-butadiene. Five Rydberg series were identified, three optically allowed (np, np, and nf_{z ³}) and two optically forbidden (ns and nd_{z ²}). It is shown that, except for the Λ～ and F? bands (which correspond to the non-valence 1 ¹B _u and the valence 2 ¹A _g states, respectively) all the transitions observed in the ultra-violet (UV) and electron-impact (EI) spectra, and in the two-photon spectra, can be assigned to members of these Rydberg series.     

Hyperfine structures and level isotope shifts of then 2 S 1/2 (n=7 – 12)- andn 2 D 3/2,5/2 (n=6 – 10)-levels of203,205Tl measured by atomic beam spectroscopy

Applying atomic beam laser spectroscopy, hyperfine constants as well as level isotope shifts of the (6s ² ns)² S _1/2 levels (n = 7 – 12) and (6s ² nd)² D _3/2,5/2 levels (n = 6 – 10) have been measured in²⁰³Tl and²⁰⁵Tl. Furthermore, some new hyperfine constants and level isotope shifts of the Tl² P _1/2,3/2-states are presented together with corrected results of earlier experiments. The hyperfine splittings have been compared with the predictions of the semiempirical theory. For theD-states a relatively poor agreement between these theoretical predictions and experimental results has been found. Using the experimental level isotope shifts and the δ〈r ²〉 value from muonic X-ray data, results of single-configuration Dirac-Fock calculations have been tested.     

Observation of forbidden (E2) lines in the ultraviolet spectra of Ca II,Sr II,and Ba II by inductively coupled plasma emission spectroscopy

Forbidden (electric quadrupole, E2) transitions of the type ns ²S_1/2–nd ²D_3/2 and ns ²S_1/2–nd ²D_5/2 in the ultraviolet spectra of singly ionized Ca, Sr, and Ba (with n = 4, 5 or 6 for Ca, Sr, and Ba, respectively) have been observed in the emission spectrum of an inductively coupled argon plasma. Wavelengths and wavenumbers of the six lines are reported and the values are in good agreement with those expected from literature data for the energy levels involved.     

Calculation of 2p 4(3 P)nl(l=s,d) Rydberg spectra of the fluorine isoelectronic sequence

The basic structure parameters of 2p ⁴(³ P)ns and 2p ⁴(³ P)nd (J=1/2, 3/2 and 5/2) Rydberg spectra for the fluorine isoelectronic sequence from FI to NiXX, as functions of effective nuclear charge, are calculated by using the eigenchannel quantum-defect theory. The results can be interpreted in terms of the variations of electrostatic and spin-orbit interactions along the sequence. A vast amount of basic atomic data can be obtained with these parameters as input. Some numerical examples are given, in which our results are in perfect agreement with experimental.     

Inner-sphere oxidation of iron(II) by tris(malonato)cobaltate(III)

The kinetics of oxidation of Fe²⁺ by [Co(C₃H₂O₄)₃]^3? in acidic solutions at 605 nm showed a simple first-order dependence in each reactant concentration. The second-order rate constant dependence on [H⁺] is in accordance with eqn (i) k₂ = k′₂ + k₃[H⁺] (i) where k′₂ and k₃ have values of 73.4 ± 14.0 M ^?1 s^?1 and 353 ± 41 M^?2 s^?1, respectively, at 1.0 M ionic strength (NaClO₄) and 25°C. At 310 nm the formation and decomposition of an intermediate, believed to be [FeC₃H₂O₄]⁺, was observed. The increase in the rate of oxidation with increasing [H⁺] was interpreted in terms of a “one-ended” dissociation mechanism which facilitates chelation of Fe₂₊ by the carbonyl oxygens of malonate in the transition state.     

Vibrational relaxation of HF(υ = 3,4)

The vibrational relaxation of pure HF(υ = 3 and υ = 4) has been studied by pumping HF directly from υ = 0 to υ = 4. The relaxation rates of υ = 3 and υ = 4 were determined to be k³_T = (2.8 ± 0.4) × 10^?11 cm³ molecule^?1 s^?1 and k⁴_T = (7.2. ± 0.5) × 10^?11 cm³ molecule^?1 s^?1 at 293 K. It is shown that sigle quantum energy transfer can account for all the vibrational relaxation.     

Preparation of polarized excited rare gas atom statesR(np 5(n+1)s) andR(np 5(n+1)p) by laser optical pumping

On the basis of rate equations we have theoretically analyzed all optical pumping schemes, which arise from the rare gas transitionsR(np ⁵(n+1)s,J _i =0, 2) toR(np ⁵(n+1)p,J _f =1, 2, 3) for linearly, circularly and unpolarized light propagating in one direction. Analytical formulae are given for the time-averaged or steady state populations of the magnetic substates and their state multipoles, as a function of the partial decay rateA _fi , the natural lifetime τ of the upper level, and the laser induced pumping rateb. Numerical values of these quantities are presented for the case of actual interestR=Ne.     

3dnl J=3e autoionizing levels of calcium: observation by laser optogalvanic spectroscopy and theoretical analysis

The even parityJ=3 autoionizing spectra of calcium were investigated below the 3d threshold by a two-step laser excitation from the 3d4s metastables through the 3d4p ³ P ₂,¹ F ₃ intermediate states. The 3d4s were populated by electronic collisions in a d.c. glow dis-charge through a Ca heat-pipe. More than a hundred resonance transitions have been measured with an accuracy of ～0.2 cm^?1 for the narrow ones using standard laser calibration techniques. Their upper levels are assigned to all expected nine autoionizing 3dns, 3dnd and 3dng Rydberg series and the 4p 5p ³ D ₃ perturber. The theoretical interpretation is achieved by a combination of the eigenchannelR-matrix and mulitchannel quantum defect (MQDT) methods. Ten closed and two openJ=3 interacting channesl are used. Theoretical energy level positions and excitation profiles are compared with the experimental data confirming the identification of the observed structures. Strong mixing between the 3d _3/2 nd _5/2 and 3d _5/2 nd _3/2 series is found, while the 3d _3/2 nd _3/2 and 3d _5/2 nd _5/2 series are almost purejj-coupled. The calculations were particularly successful in reproducing the spectrum in the region of the 4p 5p ³ D ₃ perturber, where strong chancel mixing appears leading to interference effects in the excitation cross sections.     

Vibrational-translational/rotational and vibrational-vibrational processes in methane: Optoacoustic measurements

Both V-T,R and V-V processes in methane have been studied optoacoustically following excitation of the ν₃ level with a He-Ne laser at 2947.9 cm^?1. The lifetime of the V-T,R process is 1.55 ± 0.05 μs atm. The rate constants for the fast equilibration between the bending modes is k(ν₂ → ν₄) = 60 μs^?1 atm^?1 and k(ν₄ → ν₂) = 13 μs^?1 atm^?1. The decay of the ν₃ and ν₂ stretching modes, which are in very rapid equilibrium, shows a rate constant of 0.23 ns^?1 atm^?1 and, within experimental error, produces exclusively the ν₄ stretching mode. Part of this decay, 4.6%, is by a single-quantum process producing a large amount of translational/rotational energy; the dominant process, 95.4%, is double-quantum through the 2ν₄ overtone. Both the yield of the single-quantum process and the exclusive production of the ν₄ bending mode from the (ν₃, ν₂) level are in dispute with current theoretical models.     

Spectrocoulometric study of the hydrolysis of the tris (1,10-phenanthroline)iron(III) complex ion

The spectrocoulometric technique reported earlier is applied to verify the mechanism and to evaluate the contributions k_Bi of the individual bases to the total rate constant k of the hydrolysis of the tris (1,10-phenanthroline) iron(III) complex, Fe (phen)³⁺₃. Both normal and “open-circuit” spectrocoulometric experiments are used. Partial rate constants for four bases in the acetate-buffered solutions are k_H2O=(3.4±1.2) × 10^?4s^?1 (k_H2O includes the H₂O concentration), k_OH=(1.20±0.06)×10⁷ mol^?1dm³s^?1, k_phen=(1.4±0.2) mol^?1dm³s^?1, k_Ac=(3.8±0.3)×10^?2 mol^?1dm³s^?1, at 25°C and ionic strength 0.5 mol dm^?3. The Fe(phen)³⁺³ hydrolysis, with (phen)₂ (H₂O) Fe-O-Fe (H₂O) (phen)⁴⁺² formation, is first order with respect to Fe (phen)³⁺³ and the bases present in the solution. The rate-determining step in the hydrolysis is the entry of a base to the coordinating sphere of the complex, as in the hydrolysis of the analogous 2,2′-bipyridyl complex.     

A relativistic C.I. study on theJ=1/2 even spectrum of Sr II

We present a method for performing relativistic CI calculations in ground and excited atomic and ionic levels. An electron occupying a relativistic shellnκ in a given electronic configuration is described by a single numerical four-component Dirac-Fock orbital having the samen and κ quantum numbers to those of the shellnκ. Application of this method yields estimates for the I.P. (88 741 cm^?1) and the core correlation energy (?30916 cm^?1) for Sr II and for the total correlation energy in Sr III (?30916 cm^?1). Core-valence correlation energies for the |core 5s〉 (?4379 cm^?1), |core 6s〉 (?1191 cm^?1) and |core 13s〉 (?32 cm^?1) levels have been calculated for Sr II. Estimates for the total relativistic, Breit, vacuum polarization and self energy corrections for these levels are also reported. Configurations in which the core is not fully occupied have been found to yield significant contributions to the correlation energies of both ground and excited levels. Our results show that full scale relativistic CI calculations using numerical four-component Dirac-Fock orbitals are feasible and provide a useful ab-initio tool for the investigation of atomic properties within the framework of fully relativistic theories.     

Vapor-phase electronic absorption spectrum of (η5-cyclopentadienyl)(η5-cycloheptatrienyl)chromium

The UV and visible absorption spectra of (Cp)(Ch)Cr (Cp = η⁵-C₅H₅, Ch = η⁷-C₇H₇) vapor show surprisingly well-resolved Rydberg structure. The first ionization potential (5.603 ± 0.007 eV) has been determined as a convergence limit of three Rydberg series. (Cp)(Ch)Cr is the first sandwich complex in which the lowest Rydberg transitions terminating at ns and np(σ) orbitals have vibrational structure.     

S-, O-, O,O′- p-toluenesulfinato complexes of iron(II), cobalt(II) and nickel(II) with polydentate tripod-like phosphines,crystal structure of 1,1,1-tris(diphenylphosphinomethyl)ethane p-toluenesulfinatocobalt(II) perchlorate

Reaction of sodium p-toluenesulfinate with iron(II), cobalt(II) and nickel(II) aquo ions in the presence of the poly(tertiary phosphines) 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos), tris(2-diphenylphosphinoethyl)amine (np₃) and tris(2-diphenylphosphinoethyl)phosphine (pp₃) gives five-coordinated p-toluenesulfinato complexes of formulae [(triphos)Co(p-tolSO₂)]ClO₄ and [LM(p-tolSO₂)]BPh₄ (L = pp₃, M = Fe, Co, Ni; L = np₃, M = Co, Ni). The nickel derivatives are diamagnetic with the p-toluenesulfinate ligand bonded to the metal through the sulfur atom. The iron and cobalt complexes are paramagnetic, low or high spin, with the _p-toluenesulfinate ion linked to the metal via one oxygen (np₃ and pp₃ derivatives) or both oxygen atoms (cobalt-triphosderivative).The structure of [(triphos)Co(p-tolSO₂)]ClO₄ has been determined from three-dimensional X-ray data collected by counter methods. The crystals are monoclinic, space group P2₁/n with a = 20.942(9), b =, 9.652(4), c= 22.040(8), Å, β, = 96.86(5)°, d_c = 1.407 gcm^?3 for Z = 4. Full-matrix least-squares refinements converged at the conventional R factor of 0.063 for 5573 observed reflections. The complex cation has a distorted square pyramidal geometry with the sulfinate group acting as a bidentate ligand through the two oxygen atoms.     

Ionization thresholds and positions of avoided crossing of potassium Stark Rydberg states: a Stark-adapted quantum defect orbital treatment

We have calculated the positions of the avoided level crossings between (n+2)s, np states and nd, k Stark states in the Rydberg Stark states of the potassium atom with principal quantum number n comprised between 12 and 17. We have also studied the adiabatic electric field ionization thresholds for the above Rydberg states. Both the ionization thresholds and the positions of avoided crossings have been calculated using the recently developed Stark-adapted quantum defect orbital (SQDO) formalism. The presently reported values appear to be in very good agreement with the available theoretical and experimental data.     

Lifetime of NO C2Π(υ′ = 0)

The lifetime of NO C²Π(υ′ = 0) was measured by a single photon counting technique using a nanosecond light pulser. After deconvolution, the decay rate constant of the predissociating rotational levels, (0,7 ± 0.1) x 10⁹ s^?1, and that of the non-predissociating rotational levels, (7.2 ± 2.0) x 10⁷ s^?1, were obtained. The self-quenchin rate constant for the non-predissociating levels of NO C²Π(υ′ = 0) was found to be 4.5 x 10¹¹ M^?1 s^?1.     

A relativistic CI study on OIII: wavefunctions,excitation energies and transition probabilities

The relativistic CI method is used to determine N-electron wavefunctions for the 1s ² 2s ² 2p ² (³ P ₀,³ P ₂,¹ D ₂), 1s ² 2p ^{4 3} P ₂ even levels, and the 1s ²2s2p ³ (³ D ₁,³ P ₁,³ S ₁,¹ P ₁), 1s ²2s ²2p3s (³ P ₁ and¹ P ₁), 1s ²2s ²2p3d (³ D ₁,³ P ₁,¹ P ₁)J=1 OIII levels. Excitation energies and emission probabilities between these levels are reported in the electric dipole approximation, both for the Coulomb and the Babushkin gauges.ns, p,np,nd- andnd (n17) numerical basis functions have been used for the construction of CSF's entering the CI expansion for the ASF's of these levels. Radiative matrix elements of the type calculated here within the framework of the relativistic CI method, may be used in laser assisted spectroscopic studies of atoms and ions.     

Energy and polarization dependence of chemi-ionization processes inK(42 P 3/2)−K(42 P 3/2) collisions

Using crossed molecular beams we have investigated ionizing collisions between potassium atoms in their 4² P _3/2-states, leading to the exit channelsK ₂ ⁺ +e ^?,K ⁺+K ^?, andK(4² S _1/2)+K ⁺+e ^?, respectively. Measurements of the total ionization cross section as well as of the cross sections for the individual channels are reported as a function of both the relative collision energy (0.2 to 2.4 eV) and the angle between the electric field vector of the exciting laser light and the relative velocity vector. The results are interpreted in terms of the molecular states of theK ₂ ^* quasi molecule which are involved in the ionization process.     

The influence of reagents solvation on enthalpy change of glycine-ion protonation and silver(I) glycine-ion complexation in aqueous-dimethylsulfoxide solutions

The thermal decomposition process and non-isothermal decomposition kinetic of glyphosate were studied by the Differential thermal analysis (DTA) and Thermogravimetric analysis (TGA). The results showed that the thermal decomposition temperature of glyphosate was above 198?°C. And the decomposition process was divided into three stages: The zero stage is the decomposition of impurities, and the mass loss in the first and second stage may be methylene and carbonyl, respectively. The mechanism function and kinetic parameters of non-isothermal decomposition of glyphosate were obtained from the analysis of DTA?CTG curves by the methods of Kissinger, Flynn?CWall?COzawa, Distributed activation energy model, Doyle and ?atava-?esták, respectively. In the first stage, the kinetic equation of glyphosate decomposition obtained showed that the decomposition reaction is a Valensi equation of which is two-dimensional diffusion, 2D. Its activation energy and pre-exponential factor were obtained to be 201.10?kJ?mol^?1 and 1.15?×?10¹⁹?s^?1, respectively. In the second stage, the kinetic equation of glyphosate decomposition obtained showed that the decomposition reaction is a Avrami?CErofeev equation of which is nucleation and growth, and whose reaction order (n) is 4. Its activation energy and pre-exponential factor were obtained to be 251.11?kJ?mol^?1 and 1.48?×?10²¹?s^?1, respectively. Moreover, the results of thermodynamical analysis showed that enthalpy change of ??H ^??, entropy change of ??S ^?? and the change of Gibbs free energy of ??G ^?? were, respectively, 196.80?kJ?mol^?1,107.03?J?mol^?1?K^?1, and 141.77?kJ?mol^?1 in the first stage of the process of thermal decomposition; and 246.26?kJ?mol^?1,146.43?J?mol^?1?K^?1, and 160.82?kJ?mol^?1 in the second stage.