Levelcrossing experiments in the first excited1 P 1 states of the alkaline earths

The hyperfine structure of the lowest¹P₁ state of²⁵Mg,⁴³Ca,⁸⁷Sr,¹³⁵Ba and¹³⁷Ba have been measured by the level-crossing and anticrossing technique. The magnetic dipole and electric quadrupole coupling constants determined by these measurements are²⁵Mg(3s3p¹P₁):A=? 7.7(5) MHz; 16 MHz>B>0 MHz,⁴³Ca(4s4p¹P₁):A=? 15.3(4) MHz; ¦B¦<12 MHz,⁸⁷Sr (5s5p¹P₁:A=? 3.4(4) MHz;B=39(4) MHz,¹³⁵Ba(6s6p¹P₁):A=? 97.5(1.0) MHz;B=31(9)MHz,¹³⁷Ba(6s6p¹P₁):A=?109.2(1.2) MHz;B=51(12)MHz. The results have been compared with the predictions of the Breit-Wills theory of the two-electron hyperfine structure using the experimental data on the³P states. Large discrepancies have been observed which are due to different radial wave functions of thes andp electron in the triplet and singlet system. This effect has been taken into account by fitting the data with the aid of two additional parameters. That this procedure is justified is shown by an analysis of the fine structure splitting, the life times, and the isotopic shifts in thesp configurations of group II elements.     

Doppelresonanzuntersuchungen zum Stark-Effekt des 4s 4p 3 P 1-Terms im Ca I-Spektrum

The influence of an electric field on the Zeeman-splitting of the 4s 4p ³P₁-level was investigated using the double resonance method. From the r.f.-resonance signals the tensor polarizability of the 4s 4p ³ P ₁-level was deduced to be α_ten(³ P ₁)=3.2(8) kHz/(kV/cm)². This value is used for an estimate of the oscillator strength of the infrared transition between the multiplets 4s 4p ³ P and 4s3d ³ D. Taking into account measured oscillator strengths of electric dipole transitions from the³ P ₁-level to other low lying levels one obtainsf(4s 4p ³ P→4s 3d ³ D)=0.09.     

Absolute measurement of an atomic cascade rate using a two photon coincidence technique. Application to the 4p21S0 -4s4p 1P1 -4s21S0 cascade of calcium excited by a two photon absorption

The two photon coincidence technique yields an absolute measurement of a cascade decay rate without knowing the detection efficiency of each detector. This method is applied to calcium atoms in an atomic beam excited to the 4p²¹S₀ state, and decaying via the resonant ¹P₁ state; it yields the excitation rate of the upper 4p²¹S₀ level. Since the excitation process (two photon absorption) is controlled, one can compute the excitation rate of the upper level as a function of the transition probabilities in the cascade. The lower transition is well known and we can therefore deduce the transition probability for the 4p²¹S₀ -4s4p ¹P₁, transition which previously had not been accurately determined. The preliminary measurements yield a line strength s = 0.98 ± 0.3 au in good agreement with a recent measurement of the lifetime of the 4p²¹S₀ state.     

Natural radiative lifetimes in the1 P 1 and1 F 3 sequences of Sr I

We have measured radiative lifetimes in the 5s n p ¹ P ₁ (n=5–29) and 5s n f ¹ F ₃ (n=4–11) Rydberg series in neutral strontium. The measurements were performed with single-step laser excitation starting from the ground state or from a metastable state populated by collisions. The decay photons were detected using delayed coincidence technique or a transient recorder. The presence of configuration interaction in the 5s n p ¹ P ₁ series can be observed aroundn=8. The perturbation in the 5s n f ¹ F ₃ series is not reflected in the behaviour of the lifetime values.     

Bestimmung der Lebensdauer des 3d 9 4s 4p 4 P 3/2-Terms im Cu I-Spektrum mit optischer Doppelresonanz

The lifetime of the 3d ⁹ 4s 4p ⁴ P _3/2 state of Cu has been determined with optical double resonance by observation of radiofrequency transitions ΔF=0, Δm _F =±1 between hfs-Zeeman levels of the stable odd isotopes. The result is τ(3d ⁹ 4s 4p ⁴ P _3/2, Cu)=3.18(16)·10^?7 sec.     

Optical-Optical Double Resonance Spectroscopy of the 1g(P1)-AΠ (1u)-XΣg Transition of I2

Optical-optical double resonance spectroscopy was used to study the 1_g(³P₁) ion-pair state of I₂ correlating to I⁻(¹S)+I⁺³P₁) at the dissociation limit. We gained access to the 1_g(³P₁) state though the A³Π (1_u) state in the (1+1) photon-excitation scheme. The pump laser excited the A³Π (1_u)-X¹Σ_g⁺ transition at a fixed frequency for state selection. The probe laser was scanned to detect the 1_g(³P₁)-A³Π (1_u) resonance by monitoring the ultraviolet emission from the 1_g(³P₁) state at 278 nm. The 1_g(³P₁) state was observed in a vibrational progression consisting of P and R doublets. An energy level analysis was carried out for the 1_g(³P₁) state in the 0≤ v ≤ 14 and 12≤J≤135 range, which led to a set of molecular parameters including the Ω-doubling constant. The Ω-doubling of the 1_g(³P₁) state was discussed by the pure precession model and interpreted to occur through the heterogeneous coupling with the 0_g⁻(³P₁) state correlating to the same ionic asymptote.     

Stark effect investigations of the 4f 14 6s 6p 3 P 1 and1 P 1 levels of ytterbium

The tensor polarizabilities of the 4f ¹⁴ 6s 6p ³ P ₁ level were investigated for all stable Ytterbium isotopes by the method of optical double resonance. The tensor polarizabilities were deduced from the rf-resonance signals in parallel electric and magnetic fields. The value obtained for the even Yb isotopes is in good agreement with the results derived from the measurements on the odd isotopes. The mean value isα _ten(³ P ₁)0=5.99(34)kHz/(kV/cm)². The tensor polarizability of the 4f ¹⁴ 6s 6p ¹ P ₁ level of¹⁷¹Yb was measured by means of the level crossing technique with parallel electric and magnetic fields. The experimental result isα _ten(¹ P ₁)=?14.3(1.4)kHz/(kV/cm)². This is compared with the prediction of the LS coupling approximation using the experimental data of the³ P ₁ level. Only poor agreement is obtained which is due to the configuration mixing in the¹P₁ level.     

Stark interaction in then s n p z 3 P 1 levels of zinc and cadmium

The tensor polarizabilities of then s n p z ³ P ₁ levels of Zn and Cd were measured using optical double resonance. From the rf-resonance signals in parallel electric and magnetic fields, the following tensor polarizabilities were deduced: Zn,α _ten(4s4pz ³ P ₁)=1.83(8) kHz/(kV/cm)²; Cd,α _ten(5s5pz ³ P ₁)=1.77(8) kHz/(kV/cm)². Theoretical values were calculated using Coulomb approximation. The results were then compared with previous theoretical and experimental values and, in addition, with values for Hg. Theoretical results obtained by a modified Sternheimer method (E.J. Robinson: J. Opt. Soc. Am.59, 782 (1969)) are in better agreement with the experimental values than the results of the Coulomb approximation calculations.     

Doppelresonanzexperimente zur Untersuchung der Hyperfeinstruktur des 6s6p 3 P 1-Zustandes von171Yb und173Yb

For the odd Yb isotopes¹⁷¹Yb and¹⁷³Yb the hyperfine splitting of the 6s6p ³ P ₁ state has been measured by optical double resonance in zero magnetic field. Taking into account second order corrections due to the influence of the 6¹ P ₁ and 6³ P _0,2 states, the following results for the magnetic splitting constantA and the electric quadrupole interaction constantB have been derived: A(¹⁷¹Yb)=3958.228 (60) Mc/s, A(¹⁷³Yb)=?1094.318 (35) Mc/s, S(¹⁷³Yb)=?825.904 (85) Mc/s. The hyperfine structure anomaly of the isotopes¹⁷¹Yb and^{171 173}Yb was determined to be Δ=?0.352 (10)%.     

Calculation of the hyperfine structure of the 42 S 1/2, 42 P 1/2, 42 P 3/2 states in the 3d 10 nl configuration of Cu

The hyperfine structure of the 4² S _1/2, 4² P _1/2, 4² P _3/2 states in the 3d ¹⁰ nl configuration of Cu has been evaluated using many-body perturbation theory. Polarisation effects were included in all orders and correlation to third-order. By the use of iteration methods, a large number of higher order diagrams were also included. The correlation effects between the valence electron and the 3d shell were found to be very important. The results forA(² S _1/2) andA(² P _1/2) 5827MHz and 440 MHz, respectively, are in good agreement with the experimental results, whereas the result forA(² P _3/2)=83 MHz is far from the experimental value. No explanation was found for the discrepancy. The quadrupole values were found to be ?206 mb for⁶³Cu and ?185 mb for⁶⁵Cu.     

Laser-rf double-resonance hyperfine structure measurements of the metastable 3d 4s 1 D 2 state of43Ca

The hyperfine structure of the (3(d 4s)¹ D ₂metastable state of⁴³Ca has been measured using theABMR-LIRF method (atomic beam magnetic resonance, detected by laser induced resonance fluorescence). The measurements yielded for the magnetic dipole and electric quadrupole constantsA=?17.650(2) MHz andB=?4.642(12) MHz, respectively. From the measuredB factor the spectroscopic electric quadrupole moment (uncorrected for shielding effects) has been calculated to beQ(⁴³Ca)=?0.062(12) barn. In addition, isotope shifts in the lines (3d 4s)¹ D ₂(3d 4p)¹ F ₃ ⁰ and (3d 4s)¹ D ₂(4s 5p)¹ p ₁ ⁰ for the stable calcium isotopes have been obtained by high resolution laser spectroscopy.     

Measurement of the lifetime of the3 P 2 and4 P 5/2 states in Ar16+ and Ar15+

Promptly decaying levels in Li- and Be-like Ar could be identified in the delayed x-ray and electron spectrum in addition to the four known metastable (1s2s)¹ S ₀, (1s2s)³ S ₁, (1s2p)³ P ₂, and (1s2s2p)⁴ P _5/2 states in He- and Li-like systems. The states having lifetimes of about 10^?14s still contribute to the spectrum observed 10^?9s after the ions have passed a foil. This observation is explained by cascading processes from states of high principal quantum numbern≧14. The measured lifetime of the⁴ P _5/2 state subtracting the contribution of cascades is (0.594±0.016) ns and slightly larger than the theoretically predicted value of 0.563 ns. The³ P ₂ state is depopulated at short distances behind the foil by cascading processes. Its measured lifetime of (1.44±0.08) ns compares to a theoretical value of 1.48 ns.     

Excitation transfer and quenching induced in inelastic collisions of Zn 41P1 and 43P1 atoms

Quenching of excited Zn(4¹P₁) and Zn(4³P₁) atoms by collisions with Ar, N₂, H₂, CO and CO₂ has been investigated using methods of fluorescence spectroscopy. Mixtures of Zn vapor and quenching gases topped-up with Ar to maintain constant pressure were irradiated in a quartz cell with 2139 or 3076 Å resonance radiation which excited the 4¹P₁ or the 4³P₁ state, respectively. The resulting resonance fluorescence and sensitized fluorescence were monitored in relation to the gas density. Intensity measurements yielded the following cross sections Q_tot for the overall collisional deexcitation of the ¹P₁ state, Q₃ for quenching of the ³P₁ state, and Q₁₃ for ¹P₁→³P_J excitation transfer.For N₂: Q_tot = 26, Q₃ = 4.4, Q₁₃ = 5.8; for H₂: Q_tot = 12, Q₃ = 21, Q₁₃ < 5 × 10^-3; for CO: Q_tot = 28, Q₃ = 14, Q₁₃ = 17; for CO₂: Q_tot = 76, Q₃ = 23. All values are in Ų.     

Level-crossing-Untersuchung der Hyperfeinstruktur des 3d 10 4p 2 P 3/2-Terms von Cu63 und Cu65

The level-crossing technic has been used to investigate the hyperfinestructur of the 3d ¹⁰ 4p ² P _3/2-term in Copper I by scattering the resonance line λ=3248 Å on an atomic beam of separated isotop Cu⁶³ respectively Cu⁶⁵ in an external magnetic field. From the level-crossing signals values for the magnetic dipol interaction constantsA and for the electric quadrupol interaction constantsB are deduced to beeA(Cu⁶³)=(194,72±0,15) Mc/secB(Cu⁶³)=?(28,8±0,6) Mc/secA(Cu⁶⁵)=(208,57±0,15) Mc/secB(Cu⁶⁵)=?(25,9±0,6) Mc/sec. With theA-value of the 3d ¹⁰ 4p²P_1/2-term from optical measurements the ratioA(² P _3/2)∶A(² P _1/2)≈0,4 is about twice greater than for an unperturbetalkali-like²P-term. From the width of the level-crossing signals a mean lifetime of the 3d¹⁰ 4p²P_3/2-term τ=(7,0±0,2) · 10^?9 sec is deduced.     

Ab-initio interpretation of 〈r−3〉 electronic quantities in the hfs of Mg I 3s 3p 3 P and1 P

It has been known for a long time that, in a two-electron arc spectrum, the properties of the³ P and¹ P terms of the lowests p configuration cannot be interpreted correctly in a pure-configuration model. Following the experimental determination of the hyperfine constantA(3s 3p ¹ P ₁) in Mg I by Kluge and Otten, this paper presents the ab-initio interpretation of the 〈r ^?3〉_3p hyperfine electronic quantities in 3s 3p through the use of the multiconfigurational Hartree-Fock method. It appears that taking into account the effects of the monoelectronic excitations 3s→nd, 2p→np and 3p→np leads to ab-initio evaluations in very good agreement with experiment. The case of the 3p→np excitation, to which Brillouin's theorem should apply in principle, is discussed. Using the same method, a refined evaluation is proposed for the nuclear electric-quadrupole moment of Mg²⁵ (Q=0.200 ± 0.01 barn).     

Proton magnetic resonance study of the phase transitions of [N(CH3)4]2BCl4 (B=Co, Cu, Zn, and Cd) single crystals

The proton spin-lattice relaxation rates in [N(CH₃)₄]₂BCl₄ (B=⁵⁹Co, ⁶³Cu, ⁶⁷Zn, and ¹¹³Cd) single crystals grown using the slow evaporation method were investigated over the temperature range 120-400 K. It was found that the relaxation processes of ¹H for all the [N(CH₃)₄]₂BCl₄ crystals can be described with single exponential functions. The changes in the ¹H relaxation behavior in the neighborhood of the phase transition temperatures are used to detect changes in the state of internal motion. From the ¹H spin-lattice relaxation rate measurements for [N(CH₃)₄]₂BCl₄ crystals, the activation energies were calculated for each phase. The large values of the activation energies indicate that the N(CH₃)₄ groups are significantly affected during the transitions. Although these [N(CH₃)₄]₂BCl₄ crystals all belong to the group of A₂BX₄-type crystals, their ¹H spin-lattice relaxation rates have different temperature dependences and indicate the occurrence of different molecular motions within the crystals. We additionally show for the first time that the differences in ¹H spin-lattice relaxation rates among the [N(CH₃)₄]₂BCl₄ (B=⁵⁹Co, ⁶³Cu, ⁶⁷Zn, and ¹¹³Cd) single crystals arise from differences in the electron structures of the metal ions within the series.     

Electron-vibrational energy exchange in collisions of electronically excited N2(A 3Σ u + ) molecules with Zn(X 1 S) atoms

The interaction matrix between the N₂ molecule in the X ¹Σ _g ⁺ and A ³Σ _u ⁺ states and the Zn atom in the ¹ S and ³ P states calculated earlier by the asymptotic method was used to find the rate constants for the electron-vibrational energy exchange N₂(A ³Σ _u ⁺ , v) + Zn(¹ S) → N₂(X ¹Σ ₈ ⁺ , v′) + Zn(³ P). The calculations were performed by the transition state method, and the probabilities of transitions between intersecting electron-vibrational terms of the system in motion along the reaction coordinate were determined by the Landau-Zener equation. The calculated electron excitation transfer constants between N₂(A ³Σ _u ⁺ , v = 1, 0) and Zn(¹ S) over the temperature range 300–900 K were on the order of 10^?11?10^?12 cm³/s.     

Measurements of relative transition probabilities of ns-4p,nd-4p,and nf-3d transitions in neutral potassium

Relative transition probability (A-value) measurements are reported for the ns-4p (n = 6–15), nd-4p (n = 5–13), and nf-3d (n = 7–14) series transitions in neutral potassium (KI). The results are based on intensity measurements of optically-thin KI spectral lines from a steady-state potassium emission source. The source employed was a radially-symmetric potassium-seeded argon plasmajet containing ? 5 mole per cent K-atoms. Local emission coefficients were obtained by means of the Abel transform. For the prevailing free-stream conditions (P ～ 11 torr, T ～ 3200 K, n_e ～ 10¹⁴ cm^-3), the potassium excited state populations are described by a Boltzmann distribution down to and including the ground state.The reported A-values are normalized to that of the 580.2 nm line (7s-4p_{$\text{3}\text{2}$} transition). The relative accuracy is estimated to be 5–20% for the ns-4p series and 15–25% for the nf-3d transitions. With the exception of the data for the 6s-4p and all nf-3d transitions, the measurements agree to within estimated experimental uncertainties with the values given in the NBS tabulation [Wiese et al. (1969)], although systematic differences are observed. For the exceptions noted, the measurements lie 25–50% below the relative NBS values. Comparison is also made to recent calculations of Lindgard and Nielson, and Ormonde.     

g J -Faktoren der tiefsten3 P 1-Zustände von Strontium und Barium

Theg _J -values of the lowest³ P ₁-states of Sr and Ba have been determined with optical double resonance. The measurement has been carried out by observation of radiofrequency transitionsΔm _j =± 1 between Zeeman levels of the even isotopes. Calibration of the magnetic field has been done by optical pumping of the 3²S_1/2 ground state of the sodium atom. The results are:g _j ^exp (5s 5p ³ P ₁, Sr)=1.50065(4)g _j ^exp (6s 6p ³ P ₁, Ba)=1.49651(7).     

Core polarization of the133Cs atom by the 7p electron

The hfs of the 7² P _1/2 state of Cs has been measured by optical double resonance yieldingA(7² P _1/2,¹³³Cs)=94.35 (4) MHz. The core polarization contribution to the hfs and the value 〈r ^?3〉 _j =2.54 · 10⁺²⁴ cm^?3 of the 7p electron of Cs has been calculated from the experimental data and was compared with current theories indicating still an appreciable uncertainty in the atomic wave functions of this one-electron atom.