High resolution FTIR spectroscopy of pentafluoroethane: perturbations in the Coriolis doublet of ν4 and ν13

The FTIR spectrum of pentafluoroethane (R125) was measured in the mid infrared region from 900 to 4000 cm⁻¹. Vibrational assignments for R125 are revised by comparison of previous and current experimental data with ab initio calculations at both the MP2/6-311+(d,p) and B3LYP/TZV+(3df,3p) levels of theory. High resolution FTIR spectra were recorded at room temperature and in an enclosive flow cell at a rotational temperature of 140 K. The cold spectrum was sufficiently resolved to enable rovibrational analyses of the overlapping ν₄ (1200.7341 cm⁻¹) and ν₁₃ (1223.3 cm⁻¹) bands, which have a/c hybrid and b-type character, respectively. Ground state combination differences were used to confirm assignment of 2375 lines to ν₄ (J_max = 86, K_{a max} = 50) and 2921 lines to ν₁₃ (J_max = 60, K_{a max} = 54). Effective rotational and centrifugal distortion constants were determined for ν₄, and the polarization ratio was found to be . Severe Coriolis perturbations prevent any satisfactory fit to the ν₁₃ band.     

High-resolution FTIR spectroscopy of HNSO—Analysis of the highly perturbed ν4, ν6 and 2ν5 bands

We report a rovibrational analysis of the ν₄ and ν₆ fundamentals and the 2ν₅ overtone of HNSO from high-resolution Fourier transform infrared spectra. The ν₆ band (out-of-plane bend) centred at 757.5 cm⁻¹ is c-type. The ν₄ band (HNS bend) centred at 905.9 cm⁻¹ is predominantly a-type with a very weak b-type component (). Numerous global perturbations and localized avoided crossings affecting the v₄ = 1 rotational levels were successfully treated by inclusion of Fermi and c-axis Coriolis resonance terms between v₄ = 1 and v₅ = 2, and a b-axis Coriolis resonance term between v₄ = 1 and v₆ = 1. The latter term gives rise to an avoided crossing with an extraordinary ΔK_a = 5 selection rule. The Fermi resonance between v₄ = 1 and v₅ = 2 gives rise to strong mixing of their rotational wavefunctions in the vicinity of K_a = 18. The resultant borrowing of intensity made it possible for 2ν₅ transitions in the range K_a = 16–19 to be assigned and included in a global rovibrational treatment of all three band systems.     

Rotational structure of the 000, 010, 100, 020, and 001 vibrational states of the D216O molecule: Spectroscopic assignment of rotational levels up to J, Ka = 30 and analysis of published data

The complete spectroscopic assignment of calculated Partridge-Schwenke rotational energy levels up to J, K _a = 30 is presented for the 000, 010, 100, 020, and 001 vibrational states of the D₂ ¹⁶O molecule. The nonpolynomial model of an effective rotational Hamiltonian is used to perform the assignment and to analyze the experimental energy levels available in the literature for these states. The results obtained are compared with the data calculated by other authors. The results of this study can be useful in searching for and identifying new, highly excited rotational levels of D₂ ¹⁶O, as well as in creating the databases of parameters of rovibrational transitions of the water molecule.     

Rotational energy cluster formation in XY3 molecules: Excited vibrational states of BiH3 and SbH3

Previous theoretical work on energy cluster formation at high rotational excitation in the vibrational ground state of PH₃ [S.N. Yurchenko, W. Thiel, S. Patchkovskii, P. Jensen, Phys. Chem. Chem. Phys. 7 (2005) 573] is extended to BiH₃ and SbH₃. By means of variational calculations of the rotation–vibration energies based on ab initio potential energy surfaces, we analyze the rotational energy clustering of BiH₃ and SbH₃ at J  70 for a number of vibrational states. We show that BiH₃ and SbH₃, with their pronounced local mode behaviour, exhibit cluster formation already at moderate rotational excitation. In addition, owing to its quasi-spherical-top character, BiH₃ undergoes an imperfect bifurcation at high J. This gives rise to an energy cluster type not present in PH₃ and SbH₃. We present a semi-classical approach to the construction of the rotational energy surfaces for vibrationally excited states.     

Application of the Symmetric Top Approximation to Spectroscopy of High-Temperature Water Vapor

A new model for calculating the energies of pure rotational levels of water vapor molecules treated as a symmetric top is suggested for large values of the quantum number K _a J/2 >> 1. The effective rotational constants of model representation (using the Padé form) of the ground vibrational state of the H₂O molecule are determined. The results of calculations of the rotational line intensities and positions of line centers for the suggested model are preliminarily tested with the help of the information system HOTGAS. The contribution of transitions between high rotational states to the water vapor absorption at temperatures between 1000 and 10000 K is estimated for the 8–12 m wavelength range.     

Isotopic study of the transition of calcium monomethoxide using laser excitation and population depletion spectroscopy

High resolution excitation spectra have been obtained of the 0–0 band of the transition of four isotopologues, CaO¹²CH₃, CaO¹³CH₃, CaO¹²CD₃ and CaO¹³CD₃ of calcium monomethoxide. The deuterated species were found to have unexpectedly complicated spectra, and definitive rotational assignments were possible only from investigation by optical optical double resonance (OODR) population depletion spectroscopy. This confirmed the assignment of the CaO¹²CD₃ spectrum, and proved crucial in assigning the K-structure and spin components for CaO¹³CD₃. The state was found to be well described by the symmetric rotor model with C_3v symmetry for both hydride species but, for the deuterides, the K-structure and spin rotation splittings were irregular, especially for CaO¹³CD₃ where the K = 0 and 1 levels were heavily perturbed. The changes in the A constant determined for the hydride suggest that the CH₃ umbrella opens by 0.4°, i.e., 0.2° further on excitation to the state than on excitation to the lower-lying state (geometry change established in an earlier experiment by Crozet et al. [P. Crozet, A.J. Ross, C. Linton, A.G. Adam, W.S. Hopkins, R.J. Le Roy, J. Mol. Spectrosc. 229 (2005), 224–230]).     

Fourier-transform microwave and submillimeter-wave spectroscopy of chloroiodomethane, CH2ICl

Guided by a previous microwave study (9–35 GHz), the rotational spectrum of both chlorine isotopologues of chloroiodomethane in its vibrational and electronic ground state has been re-investigated in the microwave region and extended to the millimeter/submillimeter-wave region. Weak a-type transitions have been recorded by Fourier transform microwave spectroscopy below 20 GHz whilst strong b-type rotational transitions have been recorded between 15 and 646 GHz, corresponding to energy levels with J″ ≤ 108 and . Molecular constants including those describing the hyperfine structures owing to the two halogen atoms were accurately determined for both species from the least-squares analysis of a total of 1475 distinct transition frequencies (of which 906 belong to the CH₂I³⁵Cl isotopologue). The two sets of rotational constants allowed us to derive an r₀ structure of CH₂ICl.     

Real next-to-next-to-leading-order QCD corrections to and hadroproduction in association with a photon

We update the study of the QCD corrections to direct J/ψ and hadroproduction in association with a photon in the QCD-based approach of the Colour-Singlet (CS) Model. After comparison with the recent full next-to-leading-order (NLO) computation for this process, we provide an independent confirmation to the inclusive case that NLO QCD corrections to quarkonium-production processes whose LO exhibits a non-leading P_T behaviour can be reliably computed at mid and large P_T by considering only the real emission contributions accompanied with a kinematical cut. In turn, we evaluate the leading part of the contributions, namely those coming from (J/ψ,)+γ associated with two light partons. We find that they are dominant at mid and large P_T. This confirms our expectations from the leading P_T scaling of the new topologies appearing at NNLO. We obtain that the yield from the CS becomes one order of magnitude larger than the upper value of the potential colour-octet yield. The polarisation of the quarkonia produced in association with a photon is confirmed to be longitudinal at mid and large P_T.     

Contours of constant Δ and Ψ in the 2–4 plane for the ellipsometric functions

Contour graphs of ₂ vs ₄ for different film thicknesses and a range of angles of incidence have been plotted for the ellipsometric functions Δ and Ψ in both the reflection and transmission modes. In the case of reflection ellipsometry, when the plots for Δ_R and Ψ_R are superimposed, the two sets of contours cross nearly at right angles over a large part of the field, this being indicative of the high accuracy obtainable in using this technique to determine ₄ and ₂ and hence the optical constants, n and k, for the film material. The reflection ellipsometric technique is accurate over angles of incidence between 30° and 75° and for a range of film thicknesses between λ/30 and 5λ. Transmission ellipsometry is less useful, due to anomalies in both X_s and X_p where sudden phase changes of ±π occur in regions of interest. There is also the possibility of multiple solutions, although the use of a multiangle technique would enable the “correct” values to be more easily determined.     

Dispersed fluorescence spectroscopy of S0 vibrational levels in formaldehyde-d

High resolution dispersed fluorescence (DF) spectra of excited vibrational levels in S₀ HDCO up to 10 000 cm⁻¹ energy were recorded in a free-jet expansion. Excitation to the 0₀₀ rotational level in 4⁰ and 4¹ S₁ HDCO yielded pure vibrational spectra that are free from rotational congestion. The 162 transitions (133 unique vibrational levels) assigned in these spectra have been fit to a multiresonant Hamiltonian model, which includes harmonic frequencies , anharmonic constants (x_ij), and resonance constants (K). The assigned vibrational states were fit to the model with a standard deviation of 4.02 cm⁻¹. Extensive vibrational mixing is observed throughout the spectra. Six harmonic constants, eight anharmonic constants, and four resonance constants (K_44,1, K_66,1, K_44,66, and K_33,5) were determined experimentally. The 18 experimentally determined spectroscopic constants, with the exception of and K_66,1, were found to agree within 6 cm⁻¹ of ab initio calculated values.     

Rotational and vibrational temperatures measured in a chemiluminescent flame from FTIR Bi2 emission spectra

Rotational and vibrational temperatures of the Bi₂ dimer have been measured in a chemiluminescent flame. Emission spectra of the Bi₂ a³Σ_u⁺(a₁1_u)→X¹Σ_g⁺(X0_g⁺) transition in the near-infrared region were recorded with a FTIR spectrometer. High-resolution spectra of the 0-3, 0-8, 0-9, 2-3, 4-1, 6-0, 6-1, and 7-1 bands served for the determination of the rotational temperature. It was observed that both rotational and vibrational levels are described well by Boltzmann distributions. The average rotational temperature was found to be consistent with the vibrational temperature . The study has shown that such a very heavy molecule as Bi₂ can serve for temperature measurements by optical emission as reported so far only for light molecules.     

Diffusive EPR line width behaviour in two-dimensional Cu(Hippurate)2 4H2O single crystal

X-band EPR measurements were performed at room temperature on layered Cu(Hippurate)₂4H₂O single crystals. Despite the dimeric molecular structure the EPR spectra are characteristic for individual Cu-complexes with square-pyramidal structure and g-factors: g_x=2.045, g_y=2.085 and g_z=2.346. The anticipated zero-field splitting from dimers with S=1 is averaged out by interdimer exchange coupling within the layers. The dimers in adjacent layers are not exchange coupled as we determined from the two-component EPR spectra. Thus, the crystal is an ideal 2D magnetic system and shows a strong spin diffusion effect in the EPR line width. The spin diffusion contribution to the line width is described as P(3cos²Θ−1)² with which is much higher compared to other 2D copper(II) crystals. The background line width is due to dipolar coupling and non-resolved hyperfine structure. Exchange coupling was determined from the exchange narrowing effect as of about 0.1 cm⁻¹.     

<Emphasis Type="Italic">K</Emphasis><Subscript><Emphasis Type="Italic">e</Emphasis>3</Subscript> decays and CKM unitarity

We present a detailed numerical study of the K_e3 decays to in chiral perturbation theory with virtual photons and leptons. We describe the extraction of the CKM matrix element |V_us| from the experimental K_e3 decay parameters. We propose a consistency check of the K ⁺ _e3 and K⁰_e3 data that is largely insensitive to the dominating theoretical uncertainties, in particular the contributions of . Our analysis is highly relevant in view of the recent high statistics measurement of the K ⁺ _e3 branching ratio by E865 at Brookhaven which does not indicate any significant deviation from CKM unitarity but rather a discrepancy with the present K⁰_e3 data.Received: 22 January 2004, Published online: 30 April 2004Work supported in part by IHP-RTN, Contract No. HPRN-CT2002-00311 (EURIDICE) and by Acciones Integradas, Project No. 19/2003 (Austria), HU2002-0044 (MCYT, Spain)     

Letter: Spherically Symmetric Metrics with Shear Controlling Expansion

An isotropic spatially inhomogeneous spacetime with the stress tensor satisfying the limiting case of the strong energy condition [T₀₀ + 1/2)T] = 0 in the locally inertial coordinates where the observer's four-velocity is u ^a = ₀ ^a satisfying the constraint u ^a u_a = –1 is studied. Special metrics with accelerating expansions of the inhomogeneous spacetime merely controlled by the shear are presented as an alternative model.     

Exclusive photoproduction of mesons at HERA

The exclusive photoproduction reaction γp→p has been studied with the ZEUS experiment in ep collisions at HERA using an integrated luminosity of 468 pb⁻¹. The measurement covers the kinematic range 60<W<220 GeV and Q²<1 GeV², where W is the photon–proton centre-of-mass energy and Q² is the photon virtuality. These results, which represent the analysis of the full ZEUS data sample for this channel, are compared to predictions based on perturbative QCD.     

Spherical-separability of Non-Hermitian Hamiltonians and Pseudo- PT\mathcal{PT} -symmetry

Non-Hermitian but -symmetrized spherically-separable Dirac and Schr?dinger Hamiltonians are considered. It is observed that the descendant Hamiltonians H _r , H _θ , and H _φ play essential roles and offer some “user-feriendly” options as to which one (or ones) of them is (or are) non-Hermitian. Considering a -symmetrized H _φ , we have shown that the conventional Dirac (relativistic) and Schr?dinger (non-relativistic) energy eigenvalues are recoverable. We have also witnessed an unavoidable change in the azimuthal part of the general wavefunction. Moreover, setting a possible interaction V(θ)≠0 in the descendant Hamiltonian H _θ would manifest a change in the angular θ-dependent part of the general solution too. Whilst some -symmetrized H _φ Hamiltonians are considered, a recipe to keep the regular magnetic quantum number m, as defined in the regular traditional Hermitian settings, is suggested. Hamiltonians possess properties similar to the -symmetric ones (here the non-Hermitian -symmetric Hamiltonians) are nicknamed as pseudo- -symmetric.