Investigation of the ν5 band of methylacetylene by infrared laser Stark and microwave spectroscopy

Microwave spectra have been studied in the ground and v₅ = 1 (CC stretching mode) states of methylacetylene. From these data, dipole moments and rotational and centrifugal distortion constants have been determined, as follows: μ_D⁽⁰⁾ = 0.7839 ± 0.0010 D, μ_D⁽⁵⁾ = 0.7954 ± 0.0010 D, B₅ = 8508.119 ± 0.003 MHz, D_J⁽⁵⁾ = 1.8 ± 0.2 kHz, and D_JK⁽⁵⁾ = 169 ± 1 kHz. Laser Stark spectra have been obtained for the ν₅ band of this molecule and from these spectra the following vibration-rotation parameters have been determined: ν₅⁰ = 93.27540 ± 0.00007 cm^?1, A₅ - A₀ = ?227.0 ± 2.3 MHz and D_K⁽⁵⁾ - D_K⁽⁰⁾ = ?0.05 ± 0.50 MHz. The higher-J and -K states of the v₅ = 1 state appear to be purturbed.     

Infrared diode-laser spectrum of the CH3CN ν2 band: Analysis of local resonances with ν6±1 + 2ν8±2, ν4 + ν7±1 + ν8±1, ν4 + ν6±1, ν4 + ν7±1, and 2ν70 + ν8±1 states

Fifty-one sections of infrared diode-laser spectra of acetonitrile have been measured in the region from 2283.5 to 2235.7 cm^?1. About 450 transitions belonging to the ν₂ band have been assigned for K ≦ 7 and J ≦ 44. Anomalies found in the rotational structure have been proven to be due to five local resonances. Observed transition frequencies have been fitted by a least-squares method to a model which includes Fermi-type resonances (Δk = 0, Δ? = ± 3n) with ν₆^±1 + 2ν₈^±2 and ν₄ + ν₇^±1 + ν₈^±1 states, x, y-type Coriolis resonances (Δk = ±1, Δ? = ?3n ± 1) with ν₄ + ν₆^±1 and ν₄ + ν₇^±1 + ν₈^±1 states, and a centrifugal-distortion-type resonance (Δk = ±2, Δ? = ?3n ± 2) with a 2ν₇⁰ + ν₈^±1 state. The 11 × 11 dimensional energy matrix has been diagonalized in order to obtain the perturbed energy levels. The standard deviation for the fit is 1.075 × 10^?3 cm^?1. The molecular constants determined are also listed.     

Variation of Br quadrupole coupling with isotopic substitution in methyl bromide

The J = 0 ← 1 transitions in CH₃⁷⁹Br (I), CH₃⁸¹Br (II), CD₃⁷⁹Br (III), and CD₃⁸¹Br (IV) were measured using a Stark-cell spectrometer constructed from C-band waveguide. High-resolution spectra yielded precise values for the bromine quadrupole coupling strength. Values obtained were eqQ(I) = ?577.08 ± 0.15 MHz, eqQ(II) = ?482.18 ± 0.15 MHz, eqQ(III) = ?575.66 ± 0.15 MHz, and eqQ(IV) = ?480.89 ± 0.15 MHz. The observed center frequencies for the J = 0 ← 1 transitions are ν₀(I) = 19136.35 ± 0.03 MHz, ν₀(II) = 19063.62 ± 0.03 MHz, ν₀(III) = 15429.23 ± 0.03 MHz, and ν₀(IV) = 15362.41 ± 0.03 MHz. A 0.26 ± 0.02% decrease in bromine quadrupole coupling is observed when the methyl group is fully deuterated. This is in agreement with, and supports interpretations given for, previous results on methyl chloride.     

Microwave spectrum,centrifugal distortion constants,and quadrupole coupling constants of 3-chloropyridine

The microwave spectrum of 3-chloropyridine has been measured in the frequency region of 8.2 to 18 GHz. The rotational constants, centrifugal distortion constants, and the quadrupole coupling constants for the ³⁵Cl species are A = 5839.448 ± 0.027 MHz, B = 1604.152 ± 0.005 MHz, C = 1258.327 ± 0.004 MHz, Δ_J = 0.10 ± 0.01 KHz, Δ_JK = 0.36 ± 0.09 KHz, Δ_K = 1.18 ± 0.07 KHz, δ_J = ?0.008 ± 0.005 KHz, δ_K = 0.88 ± 0.20 KHz, χ_aa = ?70.04 ± 0.38 MHz, χ_bb = 36.68 ± 0.19 MHz. The values of rotational constants and quadrupole coupling constants for the ³⁷Cl species are A = 5840.052 ± 0.034 MHz, B = 1559.354 ± 0.01 MHz, C = 1230.739 ± 0.016 MHz, χ_aa = ?54.20 ± 1.26 MHz, χ_bb = 29.49 ± 0.48 MHz. The double bond character in the CCl bond is found to be 2%. The smaller than expected value of rotational constant A points to a “fattening” of the pyridine ring about the a-axis in contrast to 2-chloropyridine, where no such substitution effect was observed.     

The reaction 36(α, γ)40Ar: γ-transition properties of resonance and bound states in 40Ar

The El character of the de-excitation of the 9 to 10 MeV states in ⁴⁰Ar has been studied through the reaction ³⁶S(α, γ)⁴⁰Ar. Angular distributions and γ-yield asymmetries of primary transitions from the E_α = 2.35 to 3.50 MeV resonances have been measured. The Doppler-shift attenuation method was used to obtain the following lifetime values: 720 ± 120fs (E_x= 2.52 MeV), 89 ±17 (3.21), 90±17(3.511), 22 ±9 (4.33), and 105 ± 17 (4.60).     

Fine and hyperfine structure of <Emphasis Type="Italic">P</Emphasis>-wave levels in muonic hydrogen

Corrections of order α ⁵ and α ⁶ are calculated for muonic hydrogen in the fine-structure interval ΔE ^fs = E(2P _3/2) − E(2P _1/2) and in the hyperfine structure of the 2P _1/2-and 2P _3/2-wave energy levels. The resulting values of ΔE ^fs = 8352.08 μeV, ΔẼ ^hfs(2P _1/2) = 7819.80 μeV, and ΔẼ ^hfs(2P _3/2) = 3248.03 μeV provide reliable guidelines in performing a comparison with relevant experimental data and in more precisely extracting the experimental value of the (2P–2S) Lamb shift in the muonic-hydrogen atom. Original Russian Text ? A.P. Martynenko, 2008, published in Yadernaya Fizika, 2008, Vol. 71, No. 1, pp. 126–136.     

Pionic x-rays and the neutron radius of 44Ca

Differences between strong interaction level shifts and widths for 2p states in pionic atoms of ^44,40Ca have been measured. Analysis in terms of an effective pion-nucleus potential leads to a difference in neutron rms radii of r_n(44)?r_n(40) = 0.05 ± 0.05 fm.     

S12-P12-lambshift in the n = 5 and n = 6 states of ionized helium

The S_{$\text{1}\text{2}$}-P_{$\text{1}\text{2}$}-splittings in the n = 5 and n = 6 states of He⁺ have been determined by an r.f. method to be (905.2 ± 1.0) MHz and (526.7 ± 2.5) MHz, respectively (theory: 906 and 524.2 MHz). The electric fields in the resonance cell and their dependence on the experimental parameters have been examined.     

Atomic beam magnetic resonance investigations in the3 F 2 Ground State of177Hf,179Hf and180Hf

The 5d ²6s ^{2 3} F ₂ ground state of¹⁷⁷Hf,¹⁷⁹Hf and¹⁸⁰Hf has been studied using the atomic beam magnetic resonance method. The atomic beam was produced by an universal evaporation technique described in a previous paper. The results are¹⁸⁰Hfg _j (³ F ₂)=0.695812 (10)¹⁷⁷Hf Δv(³ F ₂;F=11/2?F=9/2)=991.7917 (10) MHz Δv(³ F ₂;F=9/2?F=7/2)=477.0081 (10) MHz Δv(³ F ₂;F=7/2?F=5/2)=162.8890 (10) MHz¹⁷⁹HfΔv(³ F ₂;F=13/2?F=11/2)=82.1320 (10) MHz Δv(³ F ₂;F=11/2?F=9/2)=392.8498 (10) MHz. The magnetic dipole and electric quadrupole moments of the¹⁷⁷Hf and¹⁷⁹Hf nuclear ground states as calculated from these hyperfine structure measurements are the following: μ(177)=0.75(8)μ _k , Q(177)=4.34 (65) barns μ(179)=?0.61 (6)μ _k , Q(179)=4.90 (75) barns.     

Stark and Frequency Measurements in the FIR Spectrum of H2O2

The submillimeter-wave spectrum of H₂O₂has been recorded by means of a tunable FIR spectrometer. Stark measurements have been performed on three selected transitions in then= 0 state, namely, the 2₂₀–1₁₀(τ = 4 ← 2) at 1 272 297 MHz, the 8₂₆–7₁₆(τ = 1 ← 3) at 882 451 MHz, and the 9₂₈–8₁₈(τ = 1 ← 3) at 962 933 MHz. Accurate values of the transition dipole moments of the molecule have been derived by considering the interaction between the levels involved in the transition and the close near-resonant levels. About 40 new lines, belonging to the^rQ₄and^rQ₅subbranches of the rotational transitions between the lowest torsional states (τ = 1, 2, 3, 4n= 0), have been measured in the 2.8 and 3.4 THz spectral regions and analyzed together with the previously measured millimeter- and submillimeter-wave, as well as IR, transitions.     

The magnetic moments and halflives of the 5/2− states in199Hg and197Hg and the discrepancies in the experimental hyperfine fields at Hg in Fe

The Larmor-precession frequencies for¹⁹⁷Hg in Fe have been determined to beω _L = 1291 ±25 MHz at 293 K andω _L = 1334±25 MHz at 105 K. For¹⁹⁹Hg in Feω _L =1372±50 MHz has been measured at 293 K. The half-lives of the 5/2^? states in¹⁹⁷Hg and¹⁹⁹Hg have been remeasured asT _1/2(¹⁹⁷Hg)=8.1±0.16 nsec andT _1/2(¹⁹⁹Hg)=2.45±0.05 ns, respectively. The magnetic moment of the 5/2^? 158keV state in¹⁹⁹Hg was redetermined by the integral perturbed angular correlation method in an external magnetic field of 47kG asμ(5/2 ^? ) = 0.905±0.091 nm. With this new value consistency for the magnetic hyperfine fields at Hg in Fe measured with the TDPAC-method and with the NMR/ON-method is obtained. This fact is used to determine theg-factors of the 5/2^? states in¹⁹⁷Hg and¹⁹⁹Hg more precisely fromω _L -values given above:g(¹⁹⁷Hg)=0.342(6);g(¹⁹⁹Hg)=0.352(13). The magnetic moments of the first excited 2⁺ states in^198–204Hg isotopes which rely on calibrations with the¹⁹⁹Hg-g-factor, are revised.     

Phonon coupled cooperative low-spin 1A1high-spin 5T2 transition in [Fe(phen)2(NCS)2] and [Fe(phen)2(NCSe)2] crystals

Heat capacities of [Fe(phen)₂(NCS)₂] and [Fe(phen)₂(NCSe)₂] were measured between 13⁵ and 375 K. A heat capacity anomaly due to the spin-transition from low-spin ¹A₁ to high-spin π₂ electronic ground state was found at 176·29 K for the SCN-compound and at 231·26 K for the SeCN-compound, respectively. Enthalpy and entropy of transition were determined to be ΔH = 8·60 ± 0·14 kJ mol^?1 and ΔS = 48·78 ± 0·71 J K^?1 mol^?1 for the SCN-compound and ΔH = 11·60 ± 0·44 kJ mol^?1 and ΔS = 51·22 ± 2·33 J K^?1 mol^?1 for the SeCN-compound. To account for much larger value of ΔS compared with the magnetic contribution, we suggest that there is significant coupling between electronic state and phonon system. We also present a phenomenological theory based on heterophase fluctuation. Gross aspects of magnetic, spectroscopic, and thermal behaviors were satisfactorily accounted for by this model. To examine closely the transition process, infrared spectra were recorded as a function of temperature in the range 4000 ? 30 cm^?1. The spectra revealed clearly the coexistence of the ¹A₁, and the ⁵T₂ ground states around T_c.     

Fine and hyperfine structure of the 22 P term of7Li; determination of the nuclear quadrupole moment

Microwave transitions between the Zeeman split doublet states 2² P _1/2 and 2² P _3/2 of⁷Li have been measured using the optical double resonance method. The fine structure separation was determined to bev _fs=10.053.184(58) MHz. The hyperfine structure was well resolved and led to considerably improved precision of the diagonal coupling constantsa _1/2=45.914(25) MHz,a _3/2=?3.055(14) MHz,b=?0.221(29) MHz. Furthermore, the contact, spin dipolar and orbital magnetic hyperfine constants are evaluated using additional results from level crossing experiments, which are more sensitive on the non-diagonal magnetic hyperfine constanta _3/2,1/2. The results are in good agreement with recent theoretical calculations. The nuclear quadrupole moment is derived fromb to beQ(⁷Li)=?41(6) mbarn.     

The microwave spectrum of gauche-ethylamine

The microwave spectrum of the ground state of the normal species of gauche-ethylamine CH₃CH₂NH₂ and that of -NHD, -NDH, as well as -ND₂ isotopic species were measured and assigned. The ground state splits into four substates due to two internal large amplitude motions: inversion (s and a) and internal rotation (o and e) about the CN axis. Intersystem transitions due to tunneling as well as vibrational-rotational perturbations affect not only the absorption frequencies but also the Stark effect and NQHFS. The rotational constants for the two symmetrical inversion states (s) were fitted for the normal species as (all values in MHz) A^se = 32 423.470 ± 0.184, B^se = 8 942.086 ± 0.039, and C^se = 7 825.520 ± 0.048, and A^so = 32 378.733 ± 0.182, B^so = 8 940.906 ± 0.052, and C^so = 7 825.551 ± 0.042 with the interaction constants Q_a^s = 151.12 ± 0.52 and Q_b^s = 44.4 ± 7.0. The antisymmetrical inversion states (a) were fitted as A^ae = 32 423.347 ± 0.142, B^ae = 8 942.027 ± 0.029, and C^ae = 7 825.525 ± 0.031, and A^ao = 32 378.720 ± 0.142, B^ao = 8 940.984 ± 0.029, and C^ao = 7 825.573 ± 0.031 with the interaction constants Q_a^a = 167.10 ± 0.31, Q_b^a = 48.1 ± 5.4. The energy splitting due to intersion was determined (in MHz) as Δν_inv = 1 391.39 ± 0.19 and that due to internal rotation as Δν_tors = 1 170.58 ± 0.18. The cis barrier separating the two equivalent torsional states was calculated as 690 cm^?1, and the inversion barrier between the inversion states was calculated as 1400 cm^?1, both using the Dennison-Uhlenbeck model. A simple model explaining the inversion splittings of the monodeuterated species is proposed. Comparing the relative intensities for several temperatures the gauche form was observed to be energetically higher than the trans form by 110 ± 50 cm^?1. The dipole moment could only be fitted by taking into account the internal motions yielding (in Debye) μ_a^eff = 0.11 ± 0.01, μ_b^eff = 0.65 ± 0.01, and μ_c^eff = 1.014 ± 0.015. The quadrupole coupling constants (in MHz) were found as χ_aa = ?χ⁺ = 2.268 ± 0.043 and χ_bb ? χ_cc = χ^? = 3.120 ± 0.035.     

Precision lifetime measurements with the coincident high-velocity DSA method in inverse reactions

Mean lives of low-lying states of ¹⁸O, ³⁰Si, ³³S and ³⁴S have been measured with the Dopplershift attenuation method by heavy-ion bombardment of ²H and ³H targets. The γ-ray Doppler patterns are observed with a large Ge(Li) detector at 0° in coincidence with protons around 180°, so that the experiments are performed with high-velocity, mono-energetic and unidirectional beams of nuclei in well-defined excited states. Interpretation of the γ-ray patterns measured with Mg, Al, Cu and Ag as slowing-down material, with accurately known experimental stopping powers yields consistent results with small errors: ¹⁸O, τ_nm (1.98 MeV) = 2790 ± 110 fs; ³⁰Si, τ_m(2.24) = 351 ± 19 fs and τ_m(3.50) = 89 ± 8 fs; ³³S, τ_m(0.84) = 1650 ± 50 fs and τ_m(2.31) = 206 ± 8 fs; ³⁴S, τ_m(2.13) = 470 + 20 fs and τ_m(3.30) = 196 ± 13 fs. The deduced transition strengths are compared with results from large-scale shell-model calculations.     

Measurements of intensities and nitrogen-broadened linewidths in the CO fundamental at low temperatures

Intensities and nitrogen-broadened half-widths of lines R(0), R(8) and R(16) in the fundamental band of ¹²C¹⁶O have been measured at 83°K, 100°K, 150°K, 200°K and 298°K. The intensities of several other lines in the P- and R-branches of the band have also been measured at 298°K. The absolute intensity derived from the line intensity data using the Herman-Wallis formula is S^°_v = 273 ± 10 cm^-2atm^-1 at S.T.P. A separate measurement employing the Wilson-Wells-Penner-Weber method has yielded S^°_v = 277 ± 4 cm^-2 atm^-1 at S.T.P. Both of these values are within 6 per cent of most of the previously published direct measurements of this parameter. The values for the line intensities reported earlier by other authors are lower by nearly 16 per cent.     

NMR of Dy nuclei in ferromagnetic DyAl2 and Dy metal

The NMR spin echo of Dy nuclei in ferromagnetic DyAl₂ yields for the Dy¹⁶¹ hyperfine field constant, a=?845.2±0.3 MHz and quadrupolar splitting, 2P=420.0±0.3 MHz compared to a=?830.0±0.5 MHz and 2P= 387.8±0.5 MHz in ferromagnetic Dy metal. The different contributions to these parameters are discussed. A line, observed at 1273 MHz Dy metal, is attributed to Δm_I = 2 transition.     

Electronic structure of arsabenzene: Microwave spectrum,dipole moment,and nuclear quadrupole coupling constants

The microwave spectrum of arsabenzene was analyzed; a dipole transitions were observed. The following rotational constants were obtained; A = 4871.03 ± 0.18 MHz, B = 2295.87 ± 0.01 MHz, C = 1560.10 ± 0.01 MHz. The dipole moment was 1.10 ± 0.04 D. The nuclear quadrupole coupling constants due to the ⁷⁵As nucleus were χ_aa = ?186.4 ± 0.1 MHz, χ_bb = 43.5 ± 0.2 MHz, χ_cc = 142.9 ± 0.2 MHz, and the asymmetry parameter, η = 0.533 ± 0.002. Analysis of the quadrupole coupling constants indicated that the population of the 4p orbitals on arsenic decrease in the order n_a > n_b > n_c.     

A measurement of B(E3;0+ → 31−) and some E2 transition probabilities in 132, 134, 136, 138Ba using Coulomb excitation

Reduced transition probabilities, B(E2) and B(E3), have been measured for low-lying 2⁺ and 3^? states in ^{132, 134, 136, 138}Ba using Coulomb excitation by 40 MeV ¹²C ions. The B(E2) values are in general consistent with previous measurements and the B(E3;0⁺ → 3₁^?) values are 0.176 ± 0.022, 0.148 ± 0.018, 0.155 ± 0.018 and 0.133 ± 0.013 e² · b³ for ^{132, 134, 136, 138}Ba respectively. These B(E3) values correspond to about 24 to 17 W.u. and such enhancements suggest that these 3^? states have an essentially collective character which may be attributed to octupole vibrations.     

An ab initio study of ion-pair states of the Br<Subscript>2</Subscript> molecule

This contribution reports an ab initio study of 18 ion-pair states of the Br₂ molecule correlating with the Br⁺(³P_J=2,1,0,¹D₂) +Br^–(¹S₀) dissociation asymptotes. Calculations were performed on the CASSCF/CASPT2 level of theory taking into account electron correlations and with inclusion of the spinorbit coupling. Ab initio results are compared with the experiment. For gerade and ungerade ion-pair potentials, the difference between calculated and experimental values of the equilibrium internuclear distance does not exceed ΔR_e = ±0.01 and ±0.05 Å, respectively. For the states correlating to the lowest dissociation asymptote Br⁺(³P₂) + Br^–(¹S₀), the accuracy of relative energies is postilions ΔT_e ± 0.02 eV. The dipole moment functions for some transitions between the ion-pair and valence states were calculated as well.