The electric dipole moment of methyl fluoride

The Stark effect of CH₃F is extensively used as a calibration standard in laser Stark spectroscopy. The accepted value for the dipole moment of the ground vibrational state of CH₃F is less accurate than the precision of laser Stark measurements, and questions have also been raised about the literature value. New molecular beam spectroscopy measurements have been made of the ratio of the Stark effect in the J = 1, K = 1 and J = 2, K = 2 CH₃F states to that of the 01¹0 vibrational state of OCS. The results were $\text{μ}{}_{1.1}\text{(}\text{CH}{}_3\text{F}\text{)}\text{μ}{}_{010}\text{(}\text{OCS}\text{)}\text{= 2.638905(23)}$ and $\text{μ}{}_{2.2}\text{(}\text{CH}{}_3\text{F}\text{)}\text{μ}{}_{010}\text{(}\text{OCS}\text{)}\text{= 2.63894(10)}$. This produces a dipole moment of 1.85840 D with precision relative to OCS of 10 ppm and absolute accuracy of 43 ppm.     

A study of the K = 3nA1 - A2 centrifugal splitting in the 3ν2 and 4ν2 states of PH3 using a difference-frequency laser system

A frequency tunable infrared source has been constructed by using the (Ar-laser) - (dyelaser) difference frequency method developed by Pine and applied to the observation of the overtone bands of PH₃ 3ν₂ ← 0 and 4ν₂ ← ν₂ in the 3.4 μm region and 4ν₂ ← 0 in the 1.6-μm region. A Stark modulation method was used to increase the sensitivity of detection. For transitions which were well modulated, the minimum detectable absorption coefficient was estimated to be ～3 × 10^?7 cm^?1 using a 3-m cell. Emphasis was placed on the observation of the A₁-A₂ splitting for K = 3n rotational levels. For the 3ν₂ state splittings were observed for K = 3, 6, and 9 because PH₃ is a very nearly spherical top in this state. The magnitude and the J dependence of the observed K = 3n splittings have been analyzed by using a normal symmetric rotor Hamiltonian and a centrifugal distortion term of the form $\text{τ}{}_{\mathrm{xxxz}}\text{[(J}{}_{\mathrm{+}}{}^3\text{+ J}{}_{\mathrm{?}}{}^3\text{)J}{}_{\mathrm{z}}\text{+ J}{}_{\mathrm{z}}\text{(J}{}_{\mathrm{+}}{}^3\text{+ J}{}_{\mathrm{?}}{}^3\text{)]}\text{4}$.     

Susceptibilities of the S = 12 XY model on the square lattice at T = 0

For the $\text{S =}\text{1}\text{2}\text{XY}$ model at T = 0 four susceptibilities have been calculated exactly on a sequence of finite square lattices and extrapolated to the infinite square lattice. For the ferromagnet χ_zz = 0 while χ_xx ～ N^2.9; for the antiferromagnet $\text{J}{}_{\mathrm{\chi xx}}\text{N(gμ}{}_{\mathrm{<mtext>B</mtext>}}\text{)}{}^2\text{= 0.025 ± 0.002}$ and $\text{J}{}_{\mathrm{\chi xx}}\text{N(gμ}{}_{\mathrm{<mtext>B</mtext>}}\text{)}{}^2\text{= 0.13 ± 0.03}$.     

“Forbidden” rotational spectra of symmetric-top molecules: PH3 and PD3

A millimeter-wave spectrometer having a sensitivity of 4 × 10^?10 cm^?1 in the 2-mm region has been constructed for observation of extremely weak millimeter-wave spectra of gases. It has been used to measure J → J, K = 0 ← 3 transitions in PH₃ and J → J, K = 0 ← 3 as well as K = ±1 ← ±4 transitions in PD₃. The B₀ and C₀ spectral constants (in MHz) are: for PH₃, B₀ = 133 480.15 ± 0.12 and C₀ = 117 488.85 ± 0.16; for PD₃, B₀ = 69 471.10 ± 0.03 and C₀ = 58 974.37 ± 0.05. The effective ground-state values obtained for the bond angle and bond length are: for PH₃, $\text{r}{}_0\text{(}\text{A}\text{?}\text{) = 1.420}{}_0$ and $\text{α}{}_0\text{(}{}^{\mathrm{o}}\text{) = 93.34}{}_5$; for PD₃, $\text{r}{}_0\text{(}\text{A}\text{?}\text{) = 1.417}{}_6$ and $\text{α}{}_0\text{(}{}^{\mathrm{o}}\text{) = 93.35}{}_9$. The corresponding zero-point-average values were calculated to be: for PH₃, $\text{r}{}_{\mathrm{z}}\text{(}\text{A}\text{?}\text{) = 1.4269}{}_9\text{± 0.0002}$ and $\text{α}{}_{\mathrm{z}}\text{(}{}^{\mathrm{o}}\text{) = 93.228}{}_7$; for PD₃, $\text{r}{}_{\mathrm{z}}\text{(}\text{A}\text{?}\text{) = 1.4226}{}_5\text{± 0.0001}$ and $\text{α}{}_{\mathrm{z}}\text{(}{}^{\mathrm{o}}\text{) = 93.256}{}_7\text{± 0.004}$. For both species, the equilibrium values are $\text{r}{}_{\mathrm{e}}\text{(}\text{A}\text{?}\text{) = 1.4115}{}_9\text{± 0.0006}$ and $\text{α}{}_{\mathrm{e}}\text{(}{}^{\mathrm{o}}\text{) = 93.32}{}_8\text{± 0.02}$.     

Magnetic moment of the 72+[404] ground state of 10.5 h 175Ta

The magnetic hyperfine splitting ν_M = |gμ_NB_HF/h| of ${}^{175}\text{Ta}\text{(J}{}^{\mathrm{\pi }}\text{=}\text{7}\text{2}{}^{\mathrm{+}}$; $\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 10.5}\text{h}\text{)}$ in Fe has been measured with the technique of nuclear magnetic resonance on oriented nuclei as 320.4(1) MHz. With the known hyperfine field $\text{B}{}_{\mathrm{<mtext>HF</mtext>}}\text{(}\text{Ta}\text{Fe}\text{) = ?648(13)}\text{kG}$ the magnetic moment of the $\text{7}\text{2}{}^{\mathrm{+}}\text{[404]}$ ground state of ¹⁷⁵Ta is deduced to be $\text{¦μ¦ = 2.27(5)μ}{}_{\mathrm{<mtext>N</mtext>}}$.     

Nuclear magnetic moment of the 9.7 h 12− isomer 196mAu

The magnetic hyperfine splitting v_M=|gμ_NB_HF/h| of ^196mAu (j^π=12^?; configuration ¦(π$\text{11}\text{2}$($\text{v}\text{13}\text{2}{}^{\mathrm{+}}\text{)〉}{}_{12}{}^{\mathrm{?}}$; $\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 9.7}\text{h}\text{)}$ as dilute impurity in Ni has been determined with nuclear magnetic resonance on oriented nuclei as 96.0(2) MHz. With the known hyperfine field B_HF = ?264.4(3.9) kG corrected for hyperfine anomalies the g-factor and magnetic moment of ^196mAu are deduced to be |g| = 0.476(7) and |μ| = 5.72(8) μ_N. Taking into account the known magnetic properties of $\text{π}\text{1}\text{2}{}^{\mathrm{?}}$ and $\text{v}\text{13}\text{2}{}^{\mathrm{+}}$ isomeric states in the neighbouring odd Pt, Au and Hg nuclei the structure of the 12^? state is discussed.     

l-type doubling transitions in Δ states of OCS

Molecular beam electric resonance spectroscopy has been used to measure the l-type doubling transitions in carbonyl sulfide. Transitions in J = 4 to J = 20 have been observed for the (02²0) vibrational state and for J = 1 and J = 2 for the (03¹0) state. The data has been analyzed to give the v = 2 energy separation $\text{E}{}_{\mathrm{<mtext>\Delta </mtext>}}{}^0\text{- E}{}_{\mathrm{<mtext>\Sigma </mtext>}}{}^0\text{= ?5.7861(2) + 8.36(1) × 10}{}^{\mathrm{?5}}\text{J(J + 1)}\text{cm}{}^{\mathrm{?1}}$, and the vibrational dependence of q to be 86.52(9)(v₂ + 1) KHz. The dipole moment of the (02²0) vibrational state is 0.6936(3) D.     

Submillimetre cyclotron resonance of electrons in GaP

The first observation of cyclotron resonance in n-type GaP is reported. The electrons were thermally excited at a temperature of 100 K and the resonance was observed at submillimetre wavelengths (337 μm) using a pulsed magnetic field of 0–300 kG. From experiments with B∥〈100〉, 〈110〉 and 〈111〉 it was found that the transverse effective mass for electrons is $\text{m}{}^1{}_{\mathrm{\perp }}\text{= 0.25 ± 0.01 m}{}_0$ and that the anisotropy factor for the conduction band ellipsoids is K = 20⁺¹⁰_-6.     

A cubic antiferromagnet for which the ground state is known exactly

Nearest neighbour anisotropic exchange is characterized by $\text{K}{}_{\mathrm{ij}}\text{= J}{}_6\text{S}{}_{\mathrm{ix}}\text{S}{}_{\mathrm{jx}}\text{+ J}{}_{\mathrm{\perp }}\text{(S}{}_{\mathrm{iy}}\text{S}{}_{\mathrm{jy}}\text{+S}{}_{\mathrm{iz}}\text{S}{}_{\mathrm{jz}}\text{)}$ for a bond along the x-axis. For J₆ = ?J_⊥ < 0 the ground configuration of the total exchange hamiltonian is a two-sublattice antiferromagnet which is an eigenstate of the problem.     

Nuclear magnetic moment of the 3.9 s112− isomer 193mAu

The magnetic hyperfine splitting ν_M = |gμ_NB_HF/h| of ${}^{\mathrm{<mtext>193</mtext><mtext>m</mtext>}}\text{Au}\text{(j}{}^{\mathrm{\pi }}\text{=}\text{11}\text{2}{}^{\mathrm{?}}\text{, E = 290}\text{keV}$; $\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 3.9}\text{s}\text{)}$ as a dilute impurity in Ni has been measured with nuclear magnetic resonance on oriented nuclei as 226.4(2) MHz. With the known hyperfine field B_HF = ?264.4(3.9) kG corrected for hyperfine anomalies the g-factor and magnetic moment of ^193mAu are deduced to be |g| = 1.123(17) and |μ| = 6.18(9) μ_N.     

Electron exchange between Fe2+ and Fe3+ ions on octahedral sites in spinels studied by means of paramagnetic Mössbauer spectra and susceptibility measurements

Mössbauer spectra were obtained of the paramagnetic spinels $\text{Zn}{}^{\mathrm{2+}}\text{|}\text{Zn}{}^{\mathrm{2+}}{}_{\mathrm{<mtext>(1?x)</mtext><mtext>2</mtext>}}\text{Ti}{}^{\mathrm{4+}}{}_{\mathrm{<mtext>(1+x)</mtext><mtext>2</mtext>}}\text{Fe}{}^{\mathrm{3+}}{}_{\mathrm{<mtext>(1?</mtext><mtext>x)</mtext>}}\text{Fe}{}^{\mathrm{2+}}{}_{\mathrm{x}}\text{|}\text{O}{}_4$ and susceptibilities were measured. The strong difference between the paramagnetic Fe²⁺ and Fe³⁺ spectrum, due to the different quadrupole splitting, is used for the distinction between the two species. At 300 K a superposition of the Fe³⁺ and the Fe²⁺ spectra is found for most of the iron and, in addition, some continuous absorption. The latter is strongest for equal Fe³⁺ and Fe²⁺ concentration $\text{(x =}\text{1}\text{2}\text{)}$ while it disappears towards the end members (Fe³⁺ only or Fe²⁺ only) as well as with decreasing temperature (between 78 and 200 K). From this it is concluded that it arises from thermally activated electron exchange, the frequency of which passes a “critical” value of ～10⁸ sec^?1 for increasing temperature. Paramagnetic susceptibilities are found to obey a Curie-Weiss law down to low temperatures. From the dependence of the asymptotic Curie temperature on the composition the magnetic interaction parameters J₁₁ = ?1.4 K, J₂₂ = ?3.3 K and J₁₂ = + 1.6 K for the Fe³⁺Fe³⁺, Fe²⁺Fe²⁺ and Fe³⁺Fe²⁺ interactions are derived. The experimental results are discussed in terms of a hopping model with an activation energy q ～- 0.12eV and a non-equivalence of the octahedral sites expressed by a varying potential energy difference U₀ between neighbouring sites. The continuous absorption at 300 K for $\text{x =}\text{1}\text{2}$ is attributed to about 17% of the iron on sites with U₀ running from 0 to ??0.06 eV. The ferromagnetic Fe³⁺, Fe²⁺ interaction (J₁₂) is attributed to electron transfer from localized Fe²⁺ ions to Fe³⁺ neighbours via a transfer integral b of the order of 0.05 eV. The magnitudes of J₁₂ and b are tentatively explained.     

The microwave spectrum of MnO3F

The microwave spectrum of MnO₃F has been remeasured and several corrections and new results have been obtained: B₀ = 4129.141 MHz, D_J = 1.12 kHz, D_JK = 1.87 kHz; $\text{α}{}_3{}^{\mathrm{B}}\text{= 8.622}$, $\text{α}{}_5{}^{\mathrm{B}}\text{= ? 11.994}$, $\text{α}{}_6{}^{\mathrm{B}}\text{= 6.042}$, |q₅| = 16.005, and |q₆| = 8.456 MHz.     

Central peak in polaronic crystals

A possibility of the central peak appearance in crystals with low concentration of small-radius polarons is pointed out. The intensity of the central peak increases sharply with the softening of the phonon mode $\text{(ω}{}_{\mathrm{<mtext>K</mtext><mtext>0</mtext>}}\text{→ 0)}$ in the vicinity of the structural phase transition . The peak width γ₀ is determined by the probability W of the polaron hopping between the sites γ₀ = K₀²a²W.     

Electron paramagnetic resonance of 61Ni+ in CuGaS2

EPR of ⁶¹Ni⁺ doped CuGaS₂ at 4.2 K leads to the following experimental data: $\text{g = 1.918 ± 0.006 A  < 12 × 10}{}^{-4}\text{cm}{}^{-1}\text{, g}{}_{\mathrm{\perp }}\text{= 2.328±0.006 A}{}_{\mathrm{\perp }}\text{= (65±2) × 10}{}^{-4}\text{cm}{}^{-1}$. High axial field splitting of ²T₂ state stabilizes the center against Jahn-Teller interaction. Covalency reduction factor k is 0.76.     

Backward-angle high-resolution inelastic electron scattering on 40, 42, 44, 48Ca and observation of a very strong magnetic dipole ground-state transition in 48Ca

The search for magnetic dipole transitions from the ground state-even Ca isotopes to high lying J^π=1⁺ states by means of low momentum transfer but high resolution inelastic electron scattering is described. The previously detected strongly excited J^π=1⁺ state E_X=10.319 MeV [B(M1)↑=1.12±0.27μ_K²] in ⁴⁰Ca has been confirmed, but - contrary to the expectations of the independent particle shell model - only a fairly weak M1 transition is observed in ${}^{42}\text{Ca [E}{}_{\mathrm{<mtext>X</mtext>}}\text{= 11.235}\text{MeV}\text{, B(}\text{M}\text{1)↑=0.59±0.05 μ}{}^2{}_{\mathrm{<mtext>K</mtext>}}\text{]}$ and none in ⁴⁴Ca between E_{X=8.2?12.2 MeV}. In ⁴⁸Ca, however, a very strong M1 transition [B(M1) ↑ = 4.0 ± 0.3 μ²_K] to a single state at E_X=10.227 MeV has been discovered.     

A determination of the spin of the hypernucleus 12ΛB: (II). A complete analysis

The probability distribution calculated for the decay sequence ${}^{12}{}_{\mathrm{\Lambda }}\text{B(g.s.) →}{}^{12}\text{C}{}^1\text{π}{}^{\mathrm{?}}\text{→ αααπ}{}^{\mathrm{?}}$ passing through the (J^P_N) = (2⁺, 1) intermediate state ¹²C¹ (16.11 MeV) is cast in a symmetrical form and used to calculate the likelihood for $\text{J = 1}\text{relative to}\text{J = 2}\text{for}{}^{12}{}_{\mathrm{\Lambda }}\text{B(g.s.}\text{)}$ on the basis of the 85 examples available for this decay process. This procedure has optimum sensitivity, is free from the uncertainties of the comparisons previously made using only projected angular distributions, and strongly indicates that J^P = 1^? holds for ¹²_ΛB(g.s.). An appendix points out that all the data for the decay sequence passing through the (J^P_N, T) = (1⁺, 0) level of ¹²C¹ is well fitted for J = 1 if the J = 1 → J_n = 1 transition amplitude a_s1 takes a value in the range a_s1/s = 0.08 to 0.09.     

The vibrational transition moment for the ν2 bands of 14ND3 and 15ND3

Intensities were measured at high pressure (200 Torr) for blended K-multiplets in the P and R branches of the s0 → aν₂ and a0 → sν₂ bands of ¹⁴ND₃. Intensities of 55 individual lines at 10 Torr of ¹⁵ND₃ were also measured by deconvolution of the true line shape from the observed vibration-rotation spectrum and the instrumental line shape. From these results we estimate a transition moment of 0.179 ± 0.010 D for both ¹⁴ND₃ and ¹⁵ND₃. These lead to a derivative of the dipole moment, $\text{|}\text{?μ}\text{?Q}{}_2\text{| = 93}\text{cm}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{sec}{}^{\mathrm{?1}}$.     

Rotation-vibration analysis of the Coriolis-coupled ν5g, ν6g, ν8g and ν9 bands of H2CCO

Medium resolution infrared grating spectra of gaseous ketene, H₂CCO were recorded between 1000 and 400 cm^?1, both at instrument temperature (40°C) and with cooling (?40°C). Interferometric Fourier spectra were also measured at ?70°C with resolution 0.22 cm^?1 between 450 and 330 cm^?1. The K structure of the fundamentals ν₅, ν₆, ν₈, and ν₉ was assigned. These fundamentals are coupled by a-axis Coriolis interactions. These couplings were analysed on the symmetric top basis for setting up the perturbation matrix and by utilizing the K-dependent Coriolis shifts of levels. A preliminary analysis of the Coriolis intensity anomalies was also undertaken.Band center values from combination differences are $\text{ν}{}_5{}^0\text{= 587.30 (27)}$ and $\text{ν}{}_6{}^0\text{= 528.36 (39)}\text{cm}{}^{\mathrm{?1}}$. Synthetic spectra indicate the band origins of ν₈ and ν₉ to be close to 977.8 and 439.0 cm^?1, respectively. Estimates of Coriolis coupling constants obtained from synthetic spectra are $\text{ζ}{}_{58}{}^{\mathrm{a}}\text{= + 0.33 (5)}$, $\text{ζ}{}_{68}{}^{\mathrm{a}}\text{= + 0.714 (20)}$, $\text{ζ}{}_{59}{}^{\mathrm{a}}\text{= ? 0.774 (20)}$, and $\text{ζ}{}_{69}{}^{\mathrm{a}}\text{= ? 0.30 (2)}$. Approximate ratios of unperturbed vibrational transition moments obtained from spectral simulations are $\text{M}{}_8{}^0\text{:±iM}{}_5{}^0\text{:±iM}{}_6{}^0\text{:M}{}_9{}^0\text{≈ +2:?9:+10:+0.5}$.     

Ground-state properties of 3h 184Ir and 14h 185Ir

The ground-state spectroscopic quadrupole moments of ${}^{184}\text{Ir [J}{}^{\mathrm{\pi }}\text{=(5}{}^{\mathrm{\pm }}\text{);t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{=3.00]}$ and ${}^{185}\text{Ir (J}{}^{\mathrm{\pi }}\text{=}\text{5}\text{2}{}^{\mathrm{?}}\text{;t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 14}\text{h}\text{)}$ have been determined by nuclear orientation as +2.2(4) b and ?2.03(3) b, respectively. The negative QM of ¹⁸⁵Ir can be explained only by a $\text{J}{}^{\mathrm{\pi }}\text{K=}\text{5}\text{2}{}^{\mathrm{?}}\text{1}\text{2}$ ground-state configuration. The positive QM of ¹⁸⁴Ir implies K ? 4 in contradiction to expectations of K=0, 1 in analogy to ¹⁸⁶Ir.