Absorption spectra of Ni2+ in (NH4)2Mg(SO4)2·6H2O and Co2+ in Na2Zn(SO4)2·4H2O

Optical absorption spectra of Ni²⁺ in (NH₄)₂Mg(SO₄)₂·6H₂O and Co²⁺ in Na₂Zn(SO₄)₂·4H₂O single crystals have been studied at room and liquid nitrogen temperatures. From the nature and position of the observed bands, a successful interpretation could be made assuming octahedral symmetry for both the ions in the crystals. The splitting observed for ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band in Ni²⁺ and ${}^4\text{T}{}_{\mathrm{2g}}\text{(F)}$ band in Co²⁺ at liquid nitrogen temperature have been explained as due to spin-orbit interaction. The extra band observed at 16,325 cm^-1 in the case of Ni²⁺ at low temperature has been interpreted to be the superposition of vibrational mode of SO^2-₄ radical on ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band. The observed band positions in both the crystals have been fitted with four parameters B, C, Dq and ζ.     

Magnetic circular dichroism of transition metal ions in solids—II K2NaGaF6: Cr3+

The absorption and MCD spectra of the ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{a}}$ and ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{b}}$ spin-allowed transitions of Cr³⁺ in K₂NaGaF₆ are reported. It is shown that transitions to the ${}^4\text{T}{}_{\mathrm{1g}}$. states are induced by T_1u vibratio the other spin-allowed transition, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, there are three competing intensity mechanisms: electric dipole induced by T_1u vibrations, electric dipole induced by T_2u vibrations and magnetic dipole, and an estimate is made of the relative importance of these. The magnetic dipole ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^2\text{E}{}_{\mathrm{g}}$ zero-phonon line is observed to be accompanied by a vibrational sideband for which the coupling is predominantly with T_2u vibrations. Other weak transitions are observed in MCD spectra and their origin briefly discussed.     

Some effects of spin-orbit interaction on rotational levels and rotational line intensities in vibrationally unexcited 2A, 2E, and 2F electronic states of open-shell XY4 molecules

Rotational energy levels in vibronic ground states of ²A, ²E, and ²F electronic states of open-shell XY₄ molecules, as well as rotational line intensities for allowed transitions between such states, are discussed, including the effects of spin-orbit interaction and tetrahedral splittings. Jahn-Teller effects are assumed to be small, and are only taken into account implicitly, through their contributions to various parameters in the effective Hamiltonian. Qualitative information is obtained by considering several limiting-case coupling schemes among the electron spin angular momentum S, the electron orbital angular momentum L, and the pure rotational angular momentum R. These limiting cases are similar in spirit to Hund's coupling cases in diatomic molecules, but differ sufficiently from the latter to make detailed correspondences unhelpful. Quantitative information on rotational energy levels and line intensities is obtained numerically by diagonalizing a Hamiltonian matrix set up in a basis set characterized by uncoupled moleculefixed projections of S, L, and the total angular momentum J, and symmetrized so that all basis set functions belong to a definite species in the subgroup D_2d of the true point group T_d. Hamiltonian matrix elements are determined by ladder operator techniques. Three sample calculated spectra, corresponding to $\text{p(}{}^2\text{F}{}_2\text{)-s(}{}^2\text{A}{}_1\text{)}$, $\text{d(}{}^2\text{E)-p(}{}^2\text{F}{}_2\text{)}$, and $\text{d(}{}^2\text{F}{}_2\text{)-p(}{}^2\text{F}{}_2\text{)}$ are presented. As one might expect, when the spin-orbit constant A is set equal to zero, then both qualitative and quantitative aspects of the rotational-electronic problem in open-shell XY₄ molecules can be mapped easily onto discussions of the rotation-vibration problem from the CH₄ literature.     

Chemiluminescence of IF in the gas phase reaction of I2 with F2

Emission from both the state and the previously unreported $\text{A}{}^3\text{Π}{}_1$ state of IF has been observed in the gas phase reaction of I₂ with F₂ at low pressures. For the state the transition moment and vibrational populations were extracted from the spectra by a least-squares method whereby theoretical band shapes were fit to the experimental data. The effect of flow rates of reactants and Ar on the relative emission from the two electronic states, the effect of pressure on the state, and extinction of emission near 470 nm all favor the population of excited electronic states through a four-center reaction complex, rather than association of F and I atoms.It is argued that there is an avoided curve crossing between the lowest two ³Π_0⁺ states of IF, and that the ground state dissociation energy is 23 229 ± 100 cm^?1. The radiative lifetime of the state is estimated to be 10^?3 sec and to be much shorter than that of the $\text{A}{}^3\text{Π}{}_1$ state.     

Ni2+ emission in MgO,KMgF3, KZnF3 and MgF2

The emission of Ni²⁺ ions in MgO, KMgF₃, KZnF₃ and MgF₂ crystals has been investigated. The fine structure on the bands at about 20 000 cm^-1 and 13 000 cm^-1 has been studied in detail and from this and the excitation spectra these bands are assigned to ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{A}{}_{\mathrm{2g}}$ and ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{T}{}_{\mathrm{2g}}$ transitions respectively.     

Laser excitation spectra of He2

Metastable $\text{a(2sσ)}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ He₂ molecules are produced by a dc discharge in a flowing He stream. Laser excitation downstream of the discharge produces excitation spectra for a number of He₂ states. LIF spectra are observed for the $\text{(npπ)}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ series for n = 4–9, excepting 5 and the $\text{(npπ)}{}^3\text{Π}{}_{\mathrm{g}}$ series for n = 5–15.     

Laser magnetic resonance spectrum of BrO (2Π12 ← 2Π32)

Magnetic dipole transitions between the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ components of the ground electronic state of BrO have been detected using the technique of laser magnetic resonance on three CO₂ laser lines between 964 and 970 cm^?1. This is the first direct observation of the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state in BrO. The spin-orbit splitting parameter, A, is determined to be ?967.9831(2) cm^?1 for ⁷⁹Br¹⁶O and ?967.9981(2) cm^?1 for ⁸¹Br¹⁶O. Accurate values for the rotational constant $\text{B}{}^{\mathrm{<mtext>eff</mtext>}}\text{(}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}$, the hyperfine parameters ($\text{b}{}_{\mathrm{F}}\text{+}\text{2c}\text{3}$) and d, the Λ-doubling parameter p, and the Zeeman parameter g| are also determined from an analysis of the measured spectra.     

Measurement of the 2S12−2P12 splitting in the (μ−4He)+ muonic ion

The measurement of the $\text{2S}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{→ 2P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ energy transition in muonic helium is presented. The energy difference S¹ is found to be S_exp¹ = 1381.3±0.5 meV. This result agrees with the expected value $\text{S}\text{?}{}^1\text{= 1381.2±0.3}\text{meV}$ obtained assuming the previously measured value for the $\text{2S}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{→ 2P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ energy difference.     

Spectral and temperature characteristics of Cs2Na(Er,Yb, Y)Cl6 upconverters

Spectral luminescence characteristics of the Cs₂Na(Er, Yb, Y)Cl₆ type upconverter have been measured in the range 300–650 K. A nearly sixfold decrease of the emission intensity of an upconverter was observed in the green area. This emission corresponds to two luminescence transition of Er³⁺ ions: ${}^2\text{H}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>15</mtext><mtext>2</mtext>}}$ and ${}^4\text{S}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>15</mtext><mtext>2</mtext>}}$. A mechanism of the luminescence intensity decrease has been proposed, in which deexcitation of the ${}^4\text{S}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ level to the ${}^4\text{I}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ level is caused by a neighbouring Er³⁺ ion being excited to the ${}^4\text{I}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ level.     

Ultraviolet absorption spectra of Zn2 and Cd2 in solid argon and krypton at 10 K

Zinc and cadmium atoms have been condensed with argon and krypton at 10 K. The most intense absorption is due to the ${}^1\text{P}{}_1\text{←}{}^1\text{S}{}_0$ atomic transition, and a weak band is due to the ${}^3\text{P}{}_1\text{←}{}^1\text{S}{}_0$ atomic absorption. Structured absorptions at 252 and 254 nm in solid argon and krypton with vibrational spacings of 140-120 cm^?1 are due to the ${}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{←}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ transition of Zn₂. Similar 273 and 277 nm absorptions with 110-90 cm^?1 vibrational spacings are due to Cd₂ in solid argon and krypton, respectively.     

Chemical diffusion in nonstoichiometric chromium sulfide,Cr2+yS3

Using the re-equilibration kinetic method the chemical diffusion coefficient in nonstoichiometric chromium sesquisulfide, Cr_2+yS₃, has been determined as a function of temperature (1073–1373 K) and sulphur vapour pressure (10?10⁴ Pa). It has been found that this coefficient is independent of sulphur pressure and can be described by the following empirical equation: $\text{D}\text{?}\text{Cr}{}_{\mathrm{2+y}}\text{S}{}_3\text{=50.86}\text{exp(-39070 cal/mole/}\text{RT)}\text{(cm}{}^2\text{s}{}^{\mathrm{?1)}}$. It has been shown that the mobility of the point defects inCr_2+yS₃ is independent of their concentration and that the self-diffusion coefficient of chromium in this sulfide has the following function of temperature and sulphur pressure: . (cm²s^?1).     

Electrical conductivity of the system Y2O3CeO2

The electrical conductivity of the system Y₂O₃CeO₂ was measured in the temperature range 500–1100°C and P_o2 range 10^–7?10^?1 atm. Possible defect models were suggested on the basis of conductivity data, which were investigated as a function of temperature and of P_o2. The observed activation energies were 0.40 eV and 1.79 eV in the low- and high-temperature regions, respectively. The observed conductivity dependences on P_o2 were in the temperature range 500–750°C and at temperatures from 750–1100°C. It is suggested that the system Y₂O₃CeO₂ shows a mixed ionic plus hole conduction due to an O^″_i defect and an electronic hole conduction due to a V^'''_Y defect in the low- and high-temperature regions, respectively.     

Lifetime of electronic states of CO2+

The radiative lifetimes of the $\text{A}\text{?}{}^2\text{Π}{}_{\mathrm{u}}$ and $\text{B}\text{?}{}^2\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ states of CO₂⁺ were measured by means of the delayed coincidence method. Excitation was performed by a pulsed electron beam incident on CO₂. The results of these measurements are 115 ± 5 nsec for the $\text{A}\text{?}{}^2\text{Π}{}_{\mathrm{u}}$ state and 126 ± 3 nsec for the $\text{B}\text{?}{}^2\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state.     

Study of the photon spectrum in the decay KS0→π+π−γ

The branching ratio $\text{Λ(}\text{K}{}_{\mathrm{<mtext>S</mtext>}}{}^0\text{→π}{}^{\mathrm{+}}\text{π}{}^{\mathrm{?}}\text{γ)}\text{Λ(}\text{K}{}_{\mathrm{<mtext>S</mtext>}}{}^0\text{→π}{}^{\mathrm{+}}\text{π}{}^{\mathrm{?}}\text{)}$ has been determined to be (2.68±0.15)×10^?3 for photon energies $\text{E}{}_{\mathrm{\gamma }}{}^1$ greater than 50 MeV in the K_S⁰ rest frame. The decay K_S⁰→π⁺π^?γ is found to be dominated by the internal bremsstrahlung transition. The branching rato of a possible direct transition is found to be less than 0.06 × 10^?3 at 90% confidence level for $\text{E}{}_{\mathrm{\gamma }}{}^1\text{> 50}\text{MeV}$.     

Some observations on the collisional broadening and shift of the Sr 4607.33 Å line in H2/O2/Ar flames

Spectral profiles of the 4607.33 Å Sr emission line $\text{(}{}^1\text{P}{}_1\text{?}{}^1\text{S}{}_0\text{transition}\text{)}$ were measured with a pressure-scanned Fabry-Pérot interferometer in a set of pre-mixed, laminar shielded H₂/O₂/Ar flames at 1 atm with temperatures ranging from 1765 to 2365 K. Some additional integrated line profile measurements were carried out.From the full width at one-half maximum (FWHM), δλ_T, and shift of the optically thin line profiles, adiabatic cross sections for broadening and for shift were determined for SrAr and SrH₂O.     

Tabulation of hyperfine splittings in rotational F1 and F2 levels of the ground vibrational state of 12CH4 for J ≤ 20

To a good approximation, hyperfine splittings for F₁ and F₂ rotational levels of the ground vibrational state of ¹²CH₄ depend linearly on three hyperfine interaction parameters. Coefficients in these linear expressions have been computed in a relatively simple manner and tabulated for levels with 1 ≤ J ≤ 20. The hyperfine pattern for the $\text{J = 7 F}{}_2{}^{\mathrm{(2)}}$ level computed from these expressions using values for the three hyperfine interaction parameters reported recently by Yi, Ozier and Ramsey (1) agrees well with the pattern obtained from new HeNe laser measurements of Hall and Bordé (2) on the $\text{P(7) F}{}_2{}^{\mathrm{(2)}}$ line of the ν₃ band of methane.     

Dye laser site selection spectroscopy on U6+ luminescent molecular centers in LiF-U3O8 crystals

The polarized excitation and emission spectra of the U⁶⁺ molecular centers giving the most intense emission lines at 18 940 cm^?1 and 19 285 cm^?1 are presented and analyzed in detáil. From the polarization experiments, it is shown that the symmetry of the centers is C_4v and that the symmetries of the observed electronic states are Γ₂, Γ₁ and Γ₅. Finally, an electronic model is proposed which associates the emission and excitation lines of the U⁶⁺ centers in the visible region to transitions between the fundamental state $\text{Γ}{}_1\text{(6p}{}^6\text{,}{}^1\text{S)}$ and the states of the excited configuration $\text{6p}{}^5\text{(}{}^2\text{P}\text{3}\text{2}\text{) 7s}$.     

Cross sections for the quenching of the excited strontium state (51P1) measured in CO/N2O flames

The quantum efficiency of fluorescence, Y, of the 4607.33 Å Sr line $\text{(}{}^1\text{P}{}_1\text{?}{}^1\text{S}{}_0\text{transition}\text{)}$ was measured in four pre-mixed, laminar, shielded CO/N₂O flames of about 2700 K, with different quantitative compositions at 1 atm. From these data, the specific quenching cross sections for O₂, CO₂, CO and N₂ were found to be (152±20 Ų), (30±5 Ų), (49±8 Ų) and (16±3 Ų), respectively.     

Near-infrared bands of S2: 3Πgi-3Σu+ system

Vibrational and rotational analyses of the near-infrared bands of S₂ lying in the region 7440–8085 Å are reported. They form a new band system involving a ${}^3\text{Π}{}_{\mathrm{gi}}\text{-}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ transition and arise from the same initial ³Π_gi state of the ³Π_gi-³Δ_ui band system reported earlier. The analyses of the bands of this system due to the isotopic molecules ³²S³⁴S and ³⁴S₂ are also reported.     

Transverse spin correlation function of the one-dimensional spin-12 XY model

The transverse spin pair correlation function p^x_n=<S^x_mS^x_m+n>=<S^x_mS^x_m+n> is calculated exactly in the thermodynamic limit of the system described by the one-dimensional, isotropic, spin-$\text{1}\text{2}$, XY Hamiltonian

$\text{H=?2J}\text{∑}\text{l=1}\text{N}\text{(S}{}^{\mathrm{x}}{}_{\mathrm{l}}\text{S}{}^{\mathrm{x}}{}_{\mathrm{l+1}}\text{+S}{}^{\mathrm{y}}{}_{\mathrm{l}}\text{S}{}^{\mathrm{y}}{}_{\mathrm{l+1}}\text{)}$

. It is found that at absolute zero temperature (T = 0), the correlation function ρ^x_n for n ≥ 0 is given by

$\text{ρ}{}^{\mathrm{x}}{}_{\mathrm{2p}}\text{=}\text{1}\text{4}\text{2}\text{π}{}^{\mathrm{2p}}\text{Π}\text{j=1}\text{p?1}\text{4j}{}^2\text{4j}{}^2\text{?1}{}^{\mathrm{2p?2j}}\text{if}\text{n=2p}$

,

$\text{ρ}{}^{\mathrm{x}}{}_{\mathrm{2p+1}}\text{=±}\text{1}\text{4}\text{2}\text{π}{}^{\mathrm{2p+1}}\text{Π}\text{j=1}\text{p}\text{4j}{}^2\text{4j}{}^2\text{?1}{}^{\mathrm{2p+2j}}\text{if}\text{n=2p+1}$

, where the plus sign applies when J is positive and the minus sign applies when J is negative. From these the asymptotic behavior as n → ∞ of |?^x_n| at T = 0 is derived to be $\text{|ρ}{}^{\mathrm{x}}{}_{\mathrm{n}}\text{| ～}\text{a}\text{n}$ with a = 0.147088?. For finite temperatures, ρ^x_n is calculated numerically. By using the results for ?^x_n, the transverse inverse correlation length and the wavenumber dependent transverse spin pair correlation function are also calculated exactly.