New high-resolution analysis of the {ν1 + ν3} band of the NO2 isotopomer of nitrogen dioxide: Line positions and intensities

The high-resolution Fourier transform absorption spectrum of an isotopic sample of nitrogen dioxide, ¹⁵N¹⁶O₂, was recorded in the 3.4 μm region. Starting from the results of a previous study [Y. Hamada, J. Mol. Struct. 242 (1991) 367-377] a new analysis of the ν₁ + ν₃ band located at 2858.7077 cm⁻¹ has been performed. This new assignment concerns (1 0 1) energy levels involving rotational quantum numbers up to K_a = 10 and N = 54. Using a theoretical model which accounts for both the electron spin-rotation resonances within each vibrational state and the Coriolis interactions between the (1 2 0) and (1 0 1) vibrational states, the spin-rotation energy levels of the (1 0 1) vibrational state could be reproduced within their experimental uncertainty. In this way, the precise vibrational energy, rotational, spin-rotation, and coupling constants were achieved for the {(1 2 0), (1 0 1)} interacting states of ¹⁵N¹⁶O₂. Using these parameters and the transition moment operator which was obtained for the main isotopic species, ¹⁴N¹⁶O₂, a comprehensive list of the line positions and intensities was generated for the ν₁ + ν₃ band of ¹⁵N¹⁶O₂.     

A study of meson-baryon couplings in the constituent quark model

Within the framework of the constituent quark model we discuss the effects of different types of meson-baryon-baryon vertex operators on the form factors and the coupling strengths of the lowest-lying positive and negative parity non-strange baryons. We compare the quark pair creation model (³P₀-model) with the SU(6)-model in which mesons are treated as elementary fields that directly couple to the quarks. The latter model is employed both in the so-called static limit and in a modification motivated by Galilei invariance. It is demonstrated that the inclusion of non-static effects simulates some features of the³P₀ vertex. Especially the reaction πN→ππN is found to be very sensitive to the different assumptions on the dynamics of theq¯q pair creation process. More indirect hints for the internal structure of the mesons might be obtained from the predicted asymmetry for the two form factors ofN→Δ+π andΔ→N+π, which occurs in the³P₀-model, only.     

Global fittings of NNO and NNO vibrational-rotational line positions using the effective Hamiltonian approach

An effective Hamiltonian built up to sixth order in the Amat-Nielsen ordering scheme describing all rovibrational energy levels in the ground electronic state and containing in explicit form all resonance interaction terms due to the approximate relations between harmonic frequencies ω₁≈2ω₂ and ω₃≈4ω₂ was applied to model the observed rovibrational line positions (collected from the literature) of ¹⁴N¹⁵N¹⁶O and ¹⁵N¹⁴N¹⁶O isotopologues of nitrous oxide. For ¹⁴N¹⁵N¹⁶O, 124 effective Hamiltonian parameters were fitted to near 28 000 observed line positions covering the 0.8-8860 cm⁻¹ spectral range. The RMS of the weighted fit is 0.00126 cm⁻¹ and dimensionless standard deviation is 1.48. For ¹⁵N¹⁴N¹⁶O, 121 effective Hamiltonian parameters were fitted to more than 31 000 observed line positions covering the same spectral interval. The RMS of the weighted fit is 0.00185 cm⁻¹ and dimensionless standard deviation is 1.85. In both cases the models describe all available line positions with precision compatible to the measurement uncertainties. A number of local resonance perturbations was found and discussed. Among these perturbations there are interpolyad resonance Coriolis interactions. A comparison of HITRAN-2008 data with the calculations based on the fitted models is presented.     

Line mixing in the QQ sub branches of the ν1 band of methyl chloride

Line-mixing effects have been studied in the ν₁ ^QQ_K (K from 0 to 10) sub branches of methyl chloride (CH₃Cl) perturbed by nitrogen (N₂). Laboratory Fourier transform spectra have been recorded at room temperature for various pressures of atmospheric interest. In order to accurately model these spectra, a theoretical approach accounting for line-mixing effects is necessary and proposed in this study. The common model used in this work is based on the state-to-state rotational cross-sections calculated by a statistical modified exponential-gap fitting law depending on few empirical parameters. These parameters have been deduced by least-squares fitting a sum rule to the N₂-broadening coefficients modeled previously. Comparisons between experimental and calculated spectra for various ^QQ sub branches at various pressures of N₂ demonstrate the adequacy of the model as compared to the use of the Voigt profile.     

Rovibrational spectrum and potential energy surface of the N2-N2O van der Waals complex

The rovibrational spectrum of the N₂-N₂O van der Waals complex has been recorded in the N₂O ν₁ region (∼1285 cm⁻¹) using a tunable diode laser spectrometer to probe a pulsed supersonic slit jet. The observed transitions together with the data observed previously in the N₂O ν₃ region are analyzed using a Watson S-reduced asymmetric rotor Hamiltonian. The rotational and centrifugal distortion constants for the ground and excited vibrational states are accurately determined. The band-origin of the spectrum is determined to be 1285.73964(14) cm⁻¹. A restricted two-dimensional intermolecular potential energy surface for a planar structure of N₂-N₂O has been calculated at the CCSD(T) level of theory with the aug-cc-pVDZ basis sets and a set of mid-bond functions. With the intermolecular distance fixed at the ground state value R = 3.6926 Å, the potential has a global minimum with a well depth of 326.64 cm⁻¹ at θ_N2 = 11.0° and θ_N2O = 84.3° and has a saddle point with a barrier height of 204.61 cm⁻¹ at θ_N2 = 97.4° and θ_N2O = 92.2°, where θ_N2(θ_N2O) is the enclosed angle between the N-N axis (N-N-O axis) and the intermolecular axis.     

Rovibronic Levels for the (1-3)Πg Manifold of B2: Exterior Complex Scaling Finite Element Calculations Based on an Adiabatic and a Strictly Diabatic Basis

A one-dimensional complex scaled finite element method was applied on an adiabatic basis of B₂ in order to find rovibronic term energy values for the (1)³Π_g; (v, N)=(0-8, 0-25) and (2)³Π_g; (v, N)=(0-10, 0-25) levels. The method was also applied to the (1)³Π_g; (v, N)=(0-8, 0-25) and (2)³Π_g; (v, N)=(0-1, 0-25) levels in a strictly diabatic framework. Adiabatic single-channel and diabatic coupled-channel total wavefunctions were obtained and used in order to identify the vibrational levels. Comparing levels for the interacting two-state (1-2)³Π_g and three-state (1-3)³Π_g system, a constant energy shift of about 1.7 cm⁻¹ is found. Comparisons between the adiabatic Born-Oppenheimer (BO) and the diabatic (1)³Π_g; (v, N)=(0-8, 0-25) levels show differences between −20 and 7 cm⁻¹, while the corresponding shifts for the (2)³Π_g; (v, N)=(0, 0-25) and (1, 0-25) levels are about 50 and 60 cm⁻¹, respectively. A comparison between our three-state approximation and experimental observations of the (2)³Π_g-A³Π_u electronic transition shows a difference in the line positions of about 665 cm⁻¹. The calculated widths for all but the (1)³Π_g; (v, N)=(7-8, 0-25), as well as the (2)³Π_g; (v, N)=(0, 0-25) BO and diabatic rovibronic levels, have small but with N increasing predissociation rates. The (1)³Π_g; (v>8, N=0-25) BO and the (2)³Π_g; (v, N)=(1, 0-25) diabatic levels are strongly predissociated with widths ≥16 cm⁻¹.     

Measurements and theoretical calculations of N2-broadening and N2-shift coefficients in the ν2 band of CH3D

In this paper, we report measured Lorentz N₂-broadening and N₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band using a multispectrum fitting technique. These measurements were made by analyzing 11 laboratory absorption spectra recorded at 0.0056 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectra were obtained using two absorption cells with path lengths of 10.2 and 25 cm. The total sample pressures ranged from 0.98 to 402.25 Torr with CH₃D volume mixing ratios of 0.01 in nitrogen. We have been able to determine the N₂ pressure-broadening coefficients of 368 ν₂ transitions with quantum numbers as high as J″ = 20 and K = 16, where K″ = K′ ≡ K (for a parallel band). The measured N₂-broadening coefficients range from 0.0248 to 0.0742 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported N₂-induced pressure-shift coefficients vary from about −0.0003 to −0.0094 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.7%. The N₂-broadening and pressure-shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are in good overall agreement with the experimental data (8.7%). The N₂-pressure shifts whose vibrational contribution is derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D, are also in reasonable agreement with the scattered experimental data (20% in most cases).     

High sensitivity CW-cavity ring down spectroscopy of N2O near 1.5 μm (III)

We present the third part of the investigation of the high sensitivity absorption spectrum of nitrous oxide by CW-Cavity Ring Down Spectroscopy near 1.5 μm. In the two first contributions (A. Liu, et al., J. Mol. Spectrosc. 244 (2007) 33-47 and A. Liu, et al., J. Mol. Spectrosc. 244 (2007) 48-62) devoted to the 5905-6833 cm⁻¹ region, more than 9000 line positions of five isotopologues (¹⁴N₂¹⁶O, ¹⁵N¹⁴N¹⁶O, ¹⁴N¹⁵N¹⁶O, ¹⁴N₂¹⁷O and ¹⁴N₂¹⁸O), were rovibrationally assigned to a total of 115 bands, most of them being newly detected. The achieved sensitivity (α_min∼3 × 10⁻¹⁰ cm⁻¹) allowed for the detection of lines with intensity weaker than 2 × 10⁻²⁹ cm/molecule. In this contribution, the investigated region was extended up to 7066 cm⁻¹. The analysis based on the predictions of the effective Hamiltonian model has allowed assigning about 1500 transitions to 17, 1, 2 and 1 bands of the ¹⁴N₂¹⁶O, ¹⁴N¹⁵N¹⁶O, ¹⁵N¹⁴N¹⁶O and ¹⁴N₂¹⁸O isotopologues, respectively. Eleven of these 21 bands are newly reported, while the observations of the transitions are extended to higher J values for most of the others. The band by band analysis has allowed reproducing the measured line positions within the experimental uncertainty (about 1 × 10⁻³ cm⁻¹) and determining the corresponding spectroscopic parameters. A detailed analysis of the rovibrational perturbations affecting three bands of ¹⁴N₂¹⁶O is presented.     

Application of a microscopic interacting boson model to single-closed-shell nuclei

The microscopic treatment of an extended IBM including the pairing vibrational modes is applied to single-closed-shell nuclei with N = 50 or Z = 50. The low-lying spectra in the N = 50 isotones are well described in terms of the quadrupole phonon and the pairing vibration. The Sn isotopes roughly resemble the N = 50 isotones. The behavior of the 0₂⁺, 0₃⁺ and 2₁⁺ levels can be explained fairly well by the present model. Introduction of the pairing-vibrational modes into the IBM is essential for describing the single-closed-shell nuclei.     

Collective electron excitations in 3D graphite clusters

Group-theoretical analysis and subsequent quantum-chemical calculations based on the molecular orbital method applied to a cyclic model of 3D semimetallic graphite lead to a multiplet of spectroscopic combinations of Slater determinants. The transition energies ΔE between terms of the multiplet are interpreted as the energies of collective electron mesoscopic excitations ?ω in the entire set of electron states characterizing the metal-type conductivity of a cluster. The estimate ?ω～0.2ΔE(N ₀/1000)^2/3 is obtained for a cluster consisting of N ₀ primitive cells. Depending on the thermal processing, N ₀=(0.3–20)×10⁶ in pyrolytic graphite, and accordingly ?ω～(10–150) eV. In the case when the energy cannot be determined accurately, methods permitting the variation of an excitation over a wide range (such as the spectroscopy of synchrotron radiation absorption and the characteristic energy losses of charged particles) appear to be the most promising.     

Structure of even-even actinides in the interacting boson model and the N = 152 subshell closure

We show that a wide range of deformed actinides can be described in terms of an interacting boson model hamiltonian with three parameters, two of them [including the coefficient of the only SU(3) symmetry breaking term] remaining almost constant over the whole region. In addition to ground γ₁ and β₁ spectra, B(E2:0_g⁺ → 2_g⁺) values are well reproduced with no extra adjustable parameters for nuclei with 136⩽N⩽146, while for nuclei beyond N = 146 an effective boson number has to be considered in order to fit the observed in the B(E2:0⁺_g → 2⁺_g) values, which is due to the presensce of a subshell closure at N = 152. The sensitive dependence of the B(E2:0_g⁺→2_g⁺) values on the effective boson numbers is emphasized. β₁ → ground and β₁ → ground transitions are fitted by breaking the SU(3) symmetry of the E2 transition operator.     

Line mixing in the ν6Q branches of self- and nitrogen-broadened methyl bromide

Line-mixing effects are studied in the ν₆^RQ_K and ^PQ_K (K=0-6) branches of methyl bromide (CH₃Br) perturbed by nitrogen (N₂). Laboratory Fourier transform spectra have been obtained at room temperature, and for a large range of pressure values of atmospheric interest. In order to accurately model these spectra, a theoretical approach accounting for line-mixing effects is proposed. This model is based on the use of the state-to-state rotational cross-sections calculated by a statistical modified exponential-gap fitting law depending on a few empirical parameters. These parameters are deduced by adjusting the calculated diagonal elements of the relaxation matrix to the N₂-broadening coefficients, known from accurate previous measurements. Comparisons between experimental and calculated profiles for various Q branches and under various pressure conditions (0.2-1 atm) demonstrate the adequacy and consistency of the proposed model. To allow accurate laboratory measurements, line-mixing effects are also modeled in the case of self-perturbed CH₃Br.     

Instanton-induced flavour mixing in mesons

The U_L(N_f)×U_R(N_f) chiral symmetric version of the Nambu-Jona-Lasinio model is extended by the 't Hooft determinant and bosonized for an arbitrary number of flavours N_f. The resulting effective meson lagrangian is explicitly calculated to leading order in the derivatives for three flavours. The 't Hooft determinant induces flavour mixing of the mesons with diagonal flavour content (π⁰, η, η′, and their scalar chiral partners δ⁰, S, ϵ) and pushes up the physical η′-mass. The η-η′ mixing angle is found to be −31°.     

Global SO(3) × SO(3) × U(1) symmetry of the Hubbard model on bipartite lattices

In this paper the global symmetry of the Hubbard model on a bipartite lattice is found to be larger than SO(4). The model is one of the most studied many-particle quantum problems, yet except in one dimension it has no exact solution, so that there remain many open questions about its properties. Symmetry plays an important role in physics and often can be used to extract useful information on unsolved non-perturbative quantum problems. Specifically, here it is found that for on-site interaction U ≠ 0 the local SU(2) × SU(2) × U(1) gauge symmetry of the Hubbard model on a bipartite lattice with N_a^D sites and vanishing transfer integral t = 0 can be lifted to a global [SU(2) × SU(2) × U(1)]/Z₂² = SO(3) × SO(3) × U(1) symmetry in the presence of the kinetic-energy hopping term of the Hamiltonian with t > 0. (Examples of a bipartite lattice are the D-dimensional cubic lattices of lattice constant a and edge length L = N_aa for which D = 1, 2, 3,... in the number N_a^D of sites.) The generator of the new found hidden independent charge global U(1) symmetry, which is not related to the ordinary U(1) gauge subgroup of electromagnetism, is one half the rotated-electron number of singly occupied sites operator. Although addition of chemical-potential and magnetic-field operator terms to the model Hamiltonian lowers its symmetry, such terms commute with it. Therefore, its 4^N_aD energy eigenstates refer to representations of the new found global [SU(2) × SU(2) × U(1)]/Z₂² = SO(3) × SO(3) × U(1) symmetry. Consistently, we find that for the Hubbard model on a bipartite lattice the number of independent representations of the group SO(3) × SO(3) × U(1) equals the Hilbert-space dimension 4^N_aD. It is confirmed elsewhere that the new found symmetry has important physical consequences.     

A quantum mechanical mechanism for the dissociative chemisorption of N2 on metal surfaces

The time dependent Schrödinger equation was numerically solved for the transition dynamics from the N₂-metal to the N-metal to the N-metal potential energy surfaces. The resulting rapid increase of the dissociation probability (S₀) with incident kinetic energy, its saturation at high energies and vibrational enhancement are in good agreement with recent experiments. A novel explanation for the small value of S₀ is based on the high energy value of the crossing region between the two potentials, predicting that the dissociation occurs via a tunneling mechanism. Recombinative desorption experiments of ¹⁴N₂ and ¹⁵N₂ from Re(0001) are in excellent agreement with the tunneling model.     

Exotic states X ±(1600, I G (J PC)=2+ (2++)) in photoproduction reactions

It is shown that the list of unusual mesons that are planned to be studied in photoproduction reactions can be supplemented with I ^G (J ^PC)=2⁺ (2⁺⁺) exotic states X ^±(1600), which are natural to seek as manifestations of the ρ^±ρ⁰ decay channels in the reactions γN → ρ^±ρ⁰ N and γN → ρ^±ρ⁰Δ. A classification of the ρ^±ρ⁰ states according to their quantum numbers is presented. A model for the spin structure of the amplitudes for the reactions γp → f ₂(1270)p, γp → a ₂ ⁰ (1320)p, and γN → X ^±(N, Δ) is proposed, and estimates are obtained for the corresponding cross sections. At E _γ≈6 GeV, it is found that σ(γP → f ₂(1270)p)≈0.12 μb, σ(γp → a ₂ ⁰ (1320)p)≈0.25 μb, σ(γN → X ^± N → ρ^±ρ⁰ N) ≈ 0.018 μb, and σ(γp → X ⁻Δ⁺⁺ → ρ⁻ρ⁰Δ⁺⁺≈0.031 μb. The problem of isolating signals from X ^± states against the natural background that is associated with other channels of π^±π⁰π⁺π⁻ production is discussed. It is deduced that searches for exotic states X ^±(2⁺ (2⁺⁺)) in experiments at JLAB will be quite efficient—for example, the yield of about 2.8×10⁶ events per month is expected to correspond to the estimated cross sections for the reactions γN → X ^± N → ρ^±ρ⁰ N. __________ Translated from Yadernaya Fizika, Vol. 63, No. 10, 2000, pp. 1904–1912. Original Russian Text Copyright ? 2000 by Achasov, Shestakov.     

Infrared spectra of the polar and nonpolar N2O dimers in the 1280 cm region of the ν3 fundamental

The high-resolution infrared spectrum of the polar N₂O dimer has been observed in the region of the N₂O ν₃ fundamental (∼1280 cm⁻¹) using a tunable diode laser to probe a pulsed supersonic slit jet. About 120 rotational transitions were assigned in terms of an a/b hybrid band of a planar asymmetric top molecule with a slipped parallel structure. The vibrational origin was determined to be 1290.21 cm⁻¹, showing a blue shift of 5.31 cm⁻¹ with respect to the monomer band origin. In addition, the spectrum of the nonpolar isomer at 1279.71 cm⁻¹ has been remeasured and analyzed in improved detail. Small but widespread perturbations are noted in this band, which appear somewhat similar to larger effects observed previously in the ν₁ + ν₃ region for nonpolar (N₂O)₂.     

Multispectrum analysis of the ν4 band of CH3CN: Positions, intensities, self- and N2-broadening, and pressure-induced shifts

A multispectrum nonlinear least-squares fitting technique was applied to measure accurate zero-pressure line center positions, Lorentz self- and nitrogen (N₂)-broadened half-width coefficients, and self- and N₂-pressure-induced shift coefficients for over 700 transitions in the parallel ν₄ band of CH₃CN near 920 cm⁻¹. Fifteen high-resolution (0.0016 cm⁻¹) laboratory absorption spectra of pure and N₂-broadened CH₃CN recorded at room temperature using the Bruker IFS 125HR Fourier transform spectrometer located at the Pacific Northwest National Laboratory (PNNL) in Richland, Washington, USA, were analyzed simultaneously assuming standard Voigt line shapes. Short spectral intervals containing manifolds of transitions from the same value of J were fitted together. In all, high-precision line parameters were obtained for P(44)-P(3) and R(0)-R(46) manifolds. As part of the analysis, quantum assignments were extended, and the total internal partition function sum was calculated for four isotopologs: ¹²CH₃¹²CN, ¹³CH₃¹²CN, ¹²CH₃¹³CN, and ¹³CH₃¹³CN. Measurements of N₂ broadening, self-broadening, N₂-shift, and self-shift coefficients for transitions with J up to 48 and K up to 12 were measured for the first time in the mid-infrared. Self-broadened half-width coefficients were found to be very large (up to ∼2 cm⁻¹ atm⁻¹ at 296 K). Ratios of self-broadened half-width coefficients to N₂-broadened half-width coefficients show a compact distribution with rotational quantum number in both the P and R branches that range from ∼4.5 to 14 with maxima near ∣m∣=24, where m=−J″, J″, and J″+1 for P, Q, and R lines, respectively. Pressure-induced shifts for N₂ are small (few exceed ±0.006 cm⁻¹ atm⁻¹ at 294 K) and are both positive and negative. In contrast, self-shift coefficients are large (maxima of about ±0.08 cm⁻¹ atm⁻¹ at 294 K) and are both positive and negative as a function of rotational quantum numbers. The present measured half-widths and pressure shifts in ν₄ were compared with corresponding measurements of rotational transitions.     

Vibration-rotation bands of nitrous oxide: 4.1 micron region

The infrared spectrum of nitrous oxide has been measured and analyzed from 2265 cm^?1 to 2615 cm^?1. Newly refined effective rotational constants for twenty-one vibrational states of ¹⁴N₂O, three vibrational states each of ¹⁴N₂¹⁸O and ¹⁵N¹⁴N¹⁶O, two states of ¹⁴N¹⁵N¹⁶O and one state of ¹⁴N₂¹⁷O have been calculated.The most interesting features observed are two Δ-Σ “forbidden” bands, 04^2c0-00⁰0 and 12^2c0-00⁰0. These bands occur because of Coriolis interaction between unperturbed vibrational states having l = 0 and l = 2.