Measurement of multiplet intensities and noble gas-broadened line widths in the V3-fundamental of methane

Integrated intensity data at 300°K for J-multiplets between P(11)and R(11) in the _{V3-fundamental of ¹²CH4} are presented, along with the intensity of the entire Q-branch, which also encompasses the Q-branch of the _{V3-fundamental of ¹³CH4}. These data, together with theoretical estimates for the intensities of J-multiplets of J > 11, sum up to a value of S_band= 284±14cm^?2atm^?1 at 300°K. This results is in excellent agreement with most of the previously published values for this parameter. Within experimental error, the intensities of the J-multiplets in the _{V3-fundamental do not seem to exhibit the strong anamolies that were characteristic of lines in the 2V3}-band.Line widths have been measured at 100°K, 130°K, 190°K, 250°K, and 300°K for R(0), R(1), and R(2) broadened by He, Ne and Ar. The temperature dependence of the line width is discussed for the three cases of broadening. In neon broadening at 300°K, the ‘effective mean line widths’ for multiplets R(3) through R(11) have also been obtained experimentally; their J-dependence is interpreted using Gordon's theory of line shapes in multiplet spectra.     

Intensity measurements in the 2v3-band of 13CH4 at low temperatures

Absolute intensities of the J-multiplets P(1)-P(8), R(0)-R(7) and of the Q-branch in the 2v₃-band of ¹³CH₄ have been measured at 100, 150, 200, and 296°K. Our intensity data confirm the recent observation by Fox et al. that substitution of the isotope ¹³C for the central ¹²C atom in methane results in significantly different line strengths in the severely perturbed 2v₃-band. Our results at 296°K for the absolute intensities of R(0) and R(1) are in excellent agreement with the values measured by Fox et al.     

Analysis of the 2ν3 band of 12CD3F at 5.06 μm recorded under high resolution

The 2ν₃(A₁) band of ¹²CD₃F near 5.06 μm has been recorded with a resolution of 20–24 × 10^?3 cm^?1. The value of the parameter (α^B ? α^A) for this band was found to be very small and, therefore, the K structure of the R(J) and P(J) manifolds was unresolved for J < 15 and only partially resolved for larger J values. The band was analyzed using standard techniques and values for the following constants determined: ν₀ = 1977.178(3) cm^?1, B″ = 0.68216(9) cm^?1, D″_J = 1.10(30) × 10^?6 cm^?1, α^B = (B″ ? B′) = 3.086(7) × 10^?3 cm^?1, and β^J = (D″_J ? D′_J) = ?3.24(11) × 10^?7 cm^?1. A value of α^A = (A″ ? A′) = 2.90(5) × 10^?3 cm^?1 has been obtained through band contour simulations of the R(J) and P(J) multiplets.     

N2-broadening coefficients in the ν2 and ν4 bands of PH3

N₂-broadening coefficients are measured for 61 transitions of PH₃ in the ^QR branch of the ν₂ band and the ^PP, ^RP, ^SP, and ^PQ branches of the ν₄ band, using a tunable diode-laser spectrometer. The recorded lines with J values ranging from 1 to 16 and K from 0 to 11 are located between 1008 and 1106 cm⁻¹. The collisional widths are determined by fitting each spectral line with a Voigt profile, a Rautian profile, and a speed-dependent Rautian profile. The latter models provide larger broadening coefficients than the Voigt model. These coefficients have also been calculated on the basis of a semiclassical model of interacting linear molecules by considering an atom-atom Lennard-Jones potential in addition to the electrostatic contributions. The theoretical results are in good agreement with the experimental data and reproduce the J dependence of the broadenings, but their decrease at high J values is overestimated for the ^QR (J, K) transitions.     

Measurements of theg J -factors of12C in the3 P 1 and3 P 2 states

Using the atomic beam magnetic resonance method the Zeeman interactions of¹²C in the³ P ₁ and³ P ₂ states at magnetic fields of about 3.4 kOe have been measured. The measured quantities areg _J (³ P ₁)?g_J(³ P ₂)=15.4(1.0)·10^?6 g _J (³ P ₂)=1.5010616 (50), from which the following value for g_J(³P₁) can be calculated:g _J (³ P ₁)=1.5010770 (50). The experimental results are in moderate agreement with theoretical calculations.     

Amino wagging and inversion in hydrazine: K′ = 1 levels in the first excited state of the antisymmetric wagging vibration

The infrared absorption spectrum of NH₂NH₂ vapor has been observed in the region 899–1077 cm^?1, where the antisymmetric wagging band (v_a = 1 ← 0) appears, by the use of a Fourier transform spectrometer with a practical resolution of 0.003 cm^?1. In the region 925.0–925.6 cm^?1, the spectrum was also observed with a tunable diode laser, and a component, β, of the ^pQ₂ cluster has been further resolved. Most of the absorption lines assignable to β-^pP₂(J″), γ-^pP₂(J″), β-^pQ₂(J″), γ-^rQ₀(J″), β-^rR₀(J″), and γ-^rR₀(J″), where J″ = 2 ～ 15, have been identified. From these observed transition frequencies, in combination with the ground state energy levels given by microwave spectroscopy, the energy level structure of the K′ = 1 rotational states was determined. From this, the following molecular parameters for the v_a = 1 state were determined: molecular asymmetry, B′-C″ = 0.00017 cm^?1; a parameter q₅ describing an umbrella motion Coriolis interaction (q₅K) about the a axis, q₅ = ?0.0030 cm^?1; its J(J + 1) variation, q_5j = 0.00014 cm^?1; and a parameter describing an umbrella-motion K-type doubling g₅J(J + 1), g₅ = 0.000021 cm^?1.     

Level-Crossing-Untersuching der Stark-Aufspaltung der tiefsten1 P 1-Terme von Ca,Sr und Ba

Using the level-crossing technique, magnitude and sign of the tensor polarizability α_ten of the lowest¹ P ₁-levels of Ca, Sr, and Ba have been measured by investigating the splitting into Zeeman-sublevels in superimposed homogeneous electric and magnetic fields. The experimental results are: α_ten/g _J =?13.6(3) kHz/(kV/cm)² for Ca α_ten/g _J =?14.32(15) kHz/(kV/cm)² for Sr α_ten/g _J =?10.72(10) kHz/(kV/cm)² for Ba, where theg _J -values are approximatelyg _J≈1. With greater accuracy the ratios of these constants have been determined by eliminating the electric-field strength measurement: (α_ten(Sr)/g _J (Sr))/(α_ten(Ca)/g _J (Ca))=1.050(8) (α_ten(Sr)/g _J (Sr))/(α_ten(Ba)/g _J (Ba))=1.336(2). The polarizability constants are discussed with regard to the state vectors of the lowestsp ¹ P ₁- and³ P ₁-levels. The tensor polarizability of the 6s 6p¹ P ₁-level of Ba I is considered in relation to oscillator strengths of electric dipole transitions to neighbouring levels.     

Diode laser spectroscopy of the ν6 band of 13CH3l and the ν″6 band of 12CH2Dl

The ν₆ band of ¹³CH₃I and the ν″₆ band of ¹²CH₂DI have been recorded under Doppler-limited resolution in the region 820–866 cm^?1 using a tunable diode laser spectrometer. For ¹³CH₃I the constants for the ν₆ band were determined by simultaneous analysis of seven ^pQ(J,K) branches and several ^pP(J,K) and ^pR(J,K) transitions. For ¹²CH₂DI, the slight asymmetry introduced by the single D atom gives rise to noticeable asymmetry effects in the spectra of some of the ^pQ(J,K) subbands. From the analysis of six such subbands, the molecular constants for the ν″₆ level were determined.     

Theoretical absolute J-manifold intensities of the ν3 fundamental of GeH4

Theoretical absolute integrated of the J-manifolds P(1)-P(20), R(0)-R(20), and the central Q-branch in the ν₃ fundamental of GeH₄ have been projected from experimental intensity measurements. Values are presented in tabular form as a function of temperature from 200 to 340°K in 20°K increments.     

Hadronic gauge couplings in meson decays

The branching ratiosR(J→ππρ)≡Γ(J→ππρ)/Γ(J→ππ) for naturalJ ^P mesons have been evaluated under the assumption that theT(J→ππρ) amplitudes are generated by the gauge principle for ρ-mesons originally proposed by Sakurai in his approach to VMD. The ratios are predicted to increase withJ and are compatible with the present-day data. This suggests that the hadronic interactions of the photon proceed exclusively through its hadronic (VMD) component.     

Pressure broadening coefficients of transitions in the ν5 band of methyl bromide from fitting to Voigt and Galatry line profiles

Tuneable diode laser absorption spectroscopy has been used to measure the room temperature pressure broadening coefficients (γ) of rotational transitions in the v₅ fundamental band of methyl bromide (¹²CH₃⁷⁹Br and ¹²CH₃⁸¹Br) around 6.9 μm. Nitrogen, oxygen and self-broadening coefficients have been determined for 125 lines in the ^RQ₁, ^PQ₃, ^PQ₅, ^PQ₇ and ^PQ₈ branches and 49 P and R branch transitions. Line profiles within Q branches were recorded at incremental pressures of nitrogen and oxygen up to 15 Torr and fitted to a Voigt profile to yield the broadening coefficients. The nitrogen broadened data for 14 lines, chosen from the five Q branches, were also fitted with Galatry profiles. The line profiles of the P and R branch transitions were recorded for total nitrogen and oxygen pressures of up to 300 Torr and fitted to both Voigt and Galatry profiles. Within individual Q branches, nitrogen broadening coefficients were found to decrease monotonically with increasing J from 0.14 cm⁻¹ atm⁻¹ at low J to 0.09 cm⁻¹ atm⁻¹ at high J. The corresponding values for oxygen were approximately 25% smaller. Self-broadening coefficients were found to vary between 0.48 and 0.16 cm⁻¹ atm⁻¹ with a similar J dependence to the foreign gas broadening for J > 20. However, between J = 2 and J ≈ 20 the broadening coefficient was found to increase with J. The magnitude of the pressure broadening coefficient for P and R branch transitions was found to closely follow the J dependence measured for the Q branch lines.     

Bestimmung derg J-Faktoren in den Zuständen 62 P 3/2 und 82 P 3/2 von133Cs

The hyperfine structures of the 6² P _3/2- and 8² P _3/2-states of¹³³Cs have been investigated by optical double resonance in a strong magnetic field. The Landé-g-factors and the hfs coupling constants were found to be:g _J(6² P _3/2)=1.3340(3)g _J(8² P _3/2)=1.3342(2)a(6² P _3/2)=50.02(25) MHza(8² P _3/2)=7.644(25) MHz. Contrarily to recent measurements, theg _J-factors agree well with the value calculated from the Landé formula.     

Diode laser spectroscopy of the ν1-ν3 band of CF335Cl at 15.84 μm

The vibration-rotation spectrum of CF₃Cl, with natural isotopic abundance, has been recorded in the 622- to 641-cm⁻¹ region using a tunable diode laser spectrometer. The K structure of many P(J) and R(J) manifolds of the ν₁-ν₃ difference band of CF₃³⁵Cl has been resolved and positively identified. The rotational analysis has been extended in the P and R branches up to J = 39 and 47, respectively, and more than 650 lines have been assigned. A least-squares fit of the observed transitions to the energy expression including the quartic centrifugal distortion terms was performed and molecular constants for the ν₁-ν₃ difference band were determined. From the obtained parameters the ν₃ band center of CF₃³⁵Cl was evaluated as 476.9750(4) cm⁻¹ and the values of α₃^A and α₃^B were derived to be 50(1) × 10⁻⁶ and 82.9(6) × 10⁻⁶ cm⁻¹, respectively.     

Theoretical calculation of CH3Br/N2-broadening coefficients at various temperatures

The N₂-broadening coefficients of CH₃⁷⁹Br and CH₃⁸¹Br have been calculated for transitions belonging to the ^PP-, ^PQ-, ^PR-, ^RP-, ^RQ- and ^RR-branches of the ν₆ band near 10 μm, using a semiclassical impact theory. The intermolecular potential used, includes in addition to the overwhelming electrostatic interactions, induction and dispersion energy contributions, which are significant only for low J transitions with K approaching or equal to J. Comparisons have been performed with the extensive set of previous measurements at room temperature [4]. The theoretical results are in satisfactory agreement with the experimental data, and the J and K dependences are reasonably well reproduced. From calculations at 200, 230, 260 and 296 K, the temperature exponent of the collisional broadenings derived from a simple power law has been determined for each transition of each sub-branch and compared with a recent experimental evaluation [5]. Finally the N₂-broadening coefficients calculated at 296 K and their temperature exponents are given as supplementary materials of this paper for atmospheric applications and databases.     

Tunable laser Stark-difference spectra of CD3OH

We present Doppler resolution limited spectra of the P(J) and R(J) multiplets for J ≦ 10 of the 10-μm CO stretch band of ¹²CD₃¹⁶OH using a tunable diode laser. Relative frequencies within the multiplets accurate to ±0.0002–0.0005 cm^?1 are obtained, but no absolute frequencies are given. We are able to assign most of the hindered rotation and K substructure in these multiplets. The assignments are based on analyses of Stark-difference spectra combined with the ground-state microwave data and the intensity variations which are expected theoretically. The ground and excited state A, K = 1 asymmetry splitting parameters are measured to be δ₁″ = (8.5450 ± 0.0080) × 10^?3cm^?1 and δ₁′ = (9.7706 ± 0.0080) × 10^?3cm^?1, respectively. The ground-state value agrees well with the microwave results. A rapid-scan system for recording data and a computer-aided technique for calibrating and plotting the spectra are described.     

Precision measurement of theg J factors of metastable atomic states of88Sr and138Ba using the atomic beam magnetic resonance method

Theg _J factors of the metastable states³ P ₂ of⁸⁸Sr and³ D ₁,³ D ₂,³ D ₃, and¹ D ₂ of¹³⁸Ba have been measured using the atomic-beam magnetic resonance method. The metastable states were populated by an electric discharge within the atomic-beam source. From the measurements of rf transitions between the Zeeman levels (m _J =+1)?(m _J =?1) we obtained:⁸⁸Sr:g _J (³ P ₂) =1.501124(10)¹³⁸Ba:g _J (³ D ₃)=1.3340823 (10)g _J (³ D′₂)=1.1637406(11)g _J (³ D ₁)=0.4985751(13)g _J (¹ D′₂)=1.003 1449(10). The relativistic and diamagnetic corrections for theg _J factor of the³ P ₂ state of Sr have been calculated. With these and the Schwinger correction included we getg _J (³ P ₂)=1.501119(12).     

The ν1 + ν3 combination band of 238UF6

The ν₁ + ν₃ band of ²³⁸UF₆ has been observed at Doppler-limited resolution between 1291.5 and 1297.2 cm^?1 in a statically cooled longpath cell at 226 K. The frequencies of 21 transitions belonging to P(22, 28, 30), 14 belonging to R(12, 30, 31), and 28 belonging to the Q branch with 41 ≤ J ≤ 71, were measured with an accuracy of ±0.002 cm^?1. In addition, 53 frequency differences were measured in the Q branch between lines having different J assignments from Q(14) to Q(76). Five spectroscopic constants were fitted to these 116 data points with a standard deviation of 0.0006 cm^?1. The rotational constants have nearly the values expected from a consideration of ν₁ and ν₃ themselves, and there is little evidence for interaction of ν₁ + ν₃ with other levels.     

The perturbations of line frequencies in high-J manifolds of the ν3 band of SF6

In the diode laser spectra of several P- and R-branches of high-J manifolds in the ν₃ band of SF₆ it has been observed that the lines are shifted away from the positions predicted by the diagonal F_A1pp^(4,R,R) approximation of Moret-Bailly. The shifts form a smooth function of the line positions across each manifold; this function can be represented empirically by a parabola, to which the measured wavenumbers fit within experimental accuracy. This phenomenon is explained here by model calculations for P-, Q-, and R-branch excited state levels that perturb each other through higher-order vibration-rotation interactions. In the analysis, eigenvalues calculated by second-order perturbation theory are compared with those obtained by diagonalization of the Hamiltonian.     

Fine-structure splittings of excited P-and D-wave states in charmonium

It is shown that, in the relativistic case, the fine-structure splittings of the excited 2³ P _J and 3³ P _J states in charmonium are as large as those of the 1³ P _J state if the same value of α_s(μ)≈0.36 is used. The predicted mass of M(2³ P ₀)=3.84 GeV appears to be 120 MeV lower than the center of gravity of the 2³ P _J multiplet and lies below the D $\bar D$ ^* threshold. Our value of M(2³ P ₀) is nearly 80 MeV lower than that from the Godfrey and Isgur article [Phys. Rev. D 32, 189 (1985)], while the differences in other masses are not greater than 20 MeV.     

Untersuchung der Hyperfeinstruktur des 62 P 1/2-Zustandes von133Cs im starken Magnetfeld mit der optischen Doppelresonanzmethode

The hyperfine structure of the 6² P _1/2-state of¹³³Cs has been measured by optical double resonance in a strong magnetic field. From the positions of the magnetic dipole transitionsδm _J =±1,δm _I =0 theg _J -factorg _J(6² P _1/2)=0.66590(9) and the magnetic hfs-coupling constanta(6² P _1/2)=291.90(12) MHz could be derived.