The rotational spectrum of acrylonitrile in excited states of the two low-frequency CCN bending vibrational modes

The strongest vibrational satellites in the rotational spectrum of acrylonitrile have been assigned and frequencies of μ_a- and μ_b-type transitions in the frequency range 27–184 GHz are reported for the first two excited states in the lowest frequency in-plane CCN bending vibrational mode and the first excited state in the out-of-plane CCN bending mode. The values of the rotational constants, the quartic and sextic centrifugal distortion constants, and one octic centrifugal distortion constant are determined for each of these states. Less extensive results are also presented for the third quantum of the in-plane bend. The data set for the ground state has been extended by a number of new measurements and the improved ground state constants are used in a discussion of changes in rotational and centrifugal distortion constants with vibrational state where all constants associated with P_zⁿ and P²P_z⁽ⁿ⁻²⁾ terms in the Hamiltonian are found to reflect the common origin of the two CCN bends.     

The ν1 and ν3 Bands of the OOO Isotopomer of Ozone

Using 0.002 cm⁻¹ resolution Fourier transform absorption spectra of an ¹⁷O-enriched ozone sample, an extensive analysis of the ν₃ band together with a partial identification of the ν₁ band of the ¹⁷O¹⁶O¹⁷O isotopomer of ozone has been performed for the first time. As for other C_2v-type ozone isotopomers [J.-M. Flaud and R. Bacis, Spectrochim. Acta, Part A 54, 3–16 (1998)], the (001) rotational levels are involved in a Coriolis-type resonance with the levels of the (100) vibrational state. The experimental rotational levels of the (001) and (100) vibrational states have been satisfactorily reproduced using a Hamiltonian matrix which takes into account the observed rovibrational resonances. In this way precise vibrational energies and rotational and coupling constants were deduced and the following band centers ν₀(ν₃) = 1030.0946 cm⁻¹ and ν₀(ν₁) = 1086.7490 cm⁻¹ were obtained for the ν₃ and ν₁ bands, respectively.     

Vibrational kinetics of the active media of CW CO<Subscript>2</Subscript> lasers

The vibrational kinetics of CW CO₂ lasers has been analyzed within the framework of a temperature model. The necessity of taking into account the coupling of the vibrational modes of the CO₂ molecule in determining the occupation numbers and the store of vibrational energy in individual modes is shown. Expressions that connect vibrational temperatures with the rates of excitation and relaxation of the lower vibrational levels of modes have been obtained. The ratios between the vibrational temperatures on selective excitation of the 00° 1 level and on excitation of CO₂ molecules in an electric discharge as well as the character of the dependences of vibrational temperatures on the pumping-energy value are discussed.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 72–79, January–February, 2005.     

Submillimeter rotational spectrum of the formamide molecule: Ground and first excited vibrational states

The results of a study of the submillimeter rotational spectrum of formamide in states v_T=0 and 1 at frequencies of 290–500 GHz are presented. More than 300 transition frequencies are identified. Watson Hamiltonian constants are obtained for both states.Radio-Astronomy Institute, Academy of Sciences of Ukraine. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 37, No. 2, pp. 259–264, February, 1994.     

Submillimeter-wave spectroscopy of HCN in excited vibrational states

Measurements of the rotational spectrum of HCN in excited vibrational states have been extended to higher-J values. The transitions reach J=8←7 around 710 GHz for most vibrational states studied in this investigation and J=22←21 near 2 THz for the (020) and (030) vibrational states. Using a pure sample of gaseous HCN at 350 K, selected states up to one quantum in the C–H stretching vibration at 3311.5 cm⁻¹ have been investigated. Even transitions having two quanta in the C–H stretch could be studied employing a glow discharge in a gas mixture of CH₄ and N₂. Molecular constants in 13 vibrational states have been obtained, several of which have been studied for the first time by rotational spectroscopy. The vibrational temperature in the discharge system is found to be about 1500 K for the stretching vibrational modes and about 600 K for the bending states.     

Broadening and shifting of vibrational-rotational lines corresponding to the highly excited rotational states of the water molecule

Self-pressure-induced, as well as argon- and nitrogen-induced, broadening γ and shifting δ coefficients of vibrational-rotational lines of the water molecule have been calculated. The asymptotic behavior of the coefficients γ and δ at J → 42 and K _a → J has been studied. For the calculation of the parameters γ and δ, we used the wave functions obtained from the analysis of highly excited rotational states of the H₂O molecule with the maximal ever observed values of rotational quantum numbers J _max = 42, K _amax = 32. Rotational states were analyzed in the method of effective Hamiltonians using generating functions for the first eight vibrational states of the molecule.     

Calculation of the Spectroscopic Constants and Strength of the Electron Transition <Emphasis Type="Italic">A</Emphasis>0<Superscript>+</Superscript>-<Emphasis Type="Italic">X</Emphasis><Superscript>1</Superscript>Σ<Superscript>+</Superscript> of the AgAu Molecule

The vibrational, rotational, and centrifugal constants for the electronic states A and X ¹Σ⁺ of the AgAu molecule have been calculated. The calculation is based on the Morse potential functions that were used to approximate the real potential curves of the ground and excited states of AgAu. Using the experimental data on the lifetime of the vibrational levels of the excited electronic state, the strength of the A-X transition was calculated.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 176–180, March–April, 2005     

Study of processes of translational,rotational, and vibrational relaxation based on CARS spectra line shapes

This paper reviews the various physico-chemical processes responsible for actual linewidths encountered in high-resolution coherent anti-Stokes Raman spectroscopy (CARS). Most of the experimental data are based on linewidth measurements using a pulseamplified CARS spectrometer with an emission bandwidth (FWHM) of 2×10^–3 cm^–1. Detailed rotational and vibrational relaxation constants have been obtained from the analysis of theQ-branch profiles of C₂H₂, N₂, CH₄, and SiH₄.     

The H2S Spectrum around 0.7 μm

The overtone spectrum of H₂S has been recorded by intracavity laser spectroscopy in the 14100–14400 cm⁻¹spectral region. The rovibrational analysis was performed allowing one to assign not only lines involving the pair of interacting states {(402), (303)} ({(60⁺, 0), (60⁻, 0)} in local mode notation), but also lines involving the interacting states {(322), (223)} ({50⁺, 2), (50⁻, 2)} in local mode notation). Indeed, apart from the strong H₂₂interactions that link the rotational levels of the states (60^±, 0) on the one hand, and the rotational levels of the states (50⁺, 2) on the other hand, we observe that the rotational levels of the two pairs of states interact strongly through anharmonic and Coriolis-type resonances. These resonances transfer intensity to lines involving the (50⁺, 2) pair of states. Altogether 80 rotational upper-state levels have been observed and reproduced satisfactorily using an Hamiltonian matrix that takes explicitly into account the various interactions and assumes the same vibrational energy and rotational constants for the two components of the local mode pairs. The following band centers have been obtained: ν₀(60⁺, 0) = 14291.122 cm⁻¹and ν₀(50^±, 2) = 14284.705 cm⁻¹. Finally a local mode-type behavior is evidenced by the values of the Hamiltonian constants, and refined vibrational local mode parameters are obtained.     

The inter molecular potential of NH+ 4-Ar II. Calculations and experimental measurements for the rotational structure of the v 3 band

The mid-infrared spectrum of the v ₃,(t ₂) transition of the NH⁺ ₄-Ar complex has been recorded at rotational resolution using photofragmentation spectroscopy. The spectrum is divided into perpendicular and parallel subbands corresponding to transitions between different hindered internal rotor states. The P and R branches of the strongest perpendicular subbands are rotationally resolved providing rotational and centrifugal distortion constants. The widths of individual rotational lines are limited by the laser bandwidth of 0.02 cm^?1, giving a lower limit of 250 ps for the lifetime of the excited states. Effective intermolecular separations for each internal rotor state are determined from its rotational constant, after correction for the contribution due to Coriolis coupling between the internal and total rotational angular momenta. The absolute energies, rotational and distortion constants for the first few intermolecular bending and stretching levels of the ground intramolecular vibrational state are determined in a numerical solution to the rotation-intermolecular vibration Hamiltonian, employing a three-dimensional ab initio intermolecular potential. The results are compared with the experimental constants in order to assess the accuracy of the calculated potential. The relative energy levels from this calculation are also compared with those from a two-dimensional representation of the potential energy surface (‘fixed-R’ model) in order to judge directly the influence of the radial dependence of the potential.     

The rotational Raman spectra and cross sections of H2O, D2O, and HDO

We report the experimental rotational Raman spectra of H₂O, and of a mixture of D₂O and HDO in the vapor phase at room temperature, and their interpretation in terms of rotational–vibrational energies, wavefunctions, and transition moments of the molecular polarizability. These transition moments are based on high-level ab initio calculations of the wavelength dependent polarizability surface, and on wavefunctions where the rotational–vibrational coupling is considered in detail. As a byproduct of this analysis several tables have been compiled including scattering strengths and assignments for individual rotational transitions of the three species. From these tables the rotational Raman spectra can be simulated over the range of temperatures up to 2000 K for H₂O, and up to 300 K for D₂O and HDO.     

The Rotational Spectrum of H2Te

In the present work, we study the spectrum of the H₂Te molecule in the submillimeter-wave and far infrared region. An important aim of this investigation is the further experimental characterization of the anomalous “four-fold cluster effect” exhibited by the rotational energy levels in the vibrational ground state of H₂Te. The spectrum in the region 90–472 GHz was measured with a source-modulated millimeter-wave spectrometer and that between 600 and 1600 GHz with a far-infrared sideband spectrometer. The far infrared spectrum from 30 to 360 cm⁻¹was measured with a Bruker IFS 120 HR interferometer attached to a 3 m long cell. We have assigned 224 submillimeter-wave lines and 1695 FIR lines. These observed data were supplemented by a large number of ground state combination differences derived from rotation–vibration bands of H₂Te, and the resulting large data set was analyzed by means of a modified Watson Hamiltonian. Accurate sets of rotational and centrifugal distortion constants for all eight tellurium isotopomers were obtained.     

The pure rotational atmospheric lines of hydroxyl

Pure rotational line positions of the hydroxyl radical (OH) have been calculated for all vibrational levels expected in the earth's atmosphere (v = 0–9) and for lower rotational quantum numbers J″=0.5–12.5. These positions have been tabulated and compared with those derived from energy levels obtained from precise near-i.r. vibration-rotation bands and show good agreement for low J″ values. A tentative identification has been made of three v = 0 lambda-type doublets in a high-resolution far-i.r. (30–120 cm^-1) emission spectrum of the atmosphere obtained at 30 km from a balloon-borne platform. Line strength (S_J′J″) and integrated intensity (S_q cm^-2atm^-1) values have been derived for these pure rotational transitions as an aid to further work and instrument design.     

On the application of three-and five-parameter potential functions to describe the electron states of diatomic molecules

A computation of the vibrational energies and Franck-Condon factors for some electron states of N₂ and O₂ is performed in this paper by using a five-parameter Hulburt-Hirschfelder function as potential. The results obtained are compared with the results of computations with three-parameter functions selected specially for each electron state. The advantage of using these functions in comparison to the five-parameter functions to describe the electron states of diatomic molecules is shown.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 9–12, September, 1976.     

Absorption spectrum of nitrous acid for the ν1+2ν3 band studied with continuous-wave cavity ring-down spectroscopy and theoretical calculations

We present the high resolution absorption measurements of gaseous HONO at room temperature using continuous-wave cavity ring-down spectroscopy in the near-infrared region between 6017 and 6067 cm⁻¹ at a resolution of 1 pm (0.037 cm⁻¹). For the trans-HONO isomer an extensive analysis of the ν₁+2ν₃ combination band 6045.8089 cm^–1 was performed starting from the results of a previous study for the 1¹ and 3¹ vibrational states [Guilmot J-M, Godefroid M, Herman M. Rovibrational parameters for trans-nitrous acid. J Mol Spectrosc 1993;160:387–400]. The present combination band is perturbed because of the existence of several dark states of HONO which could not be identified unambiguously. The rotational constants achieved for the 1¹3² state deviate slightly from the values which are predicted from the rotational constants achieved in the previous studies for the 1¹ and 3¹ vibrational states of trans-HONO.     

Asymptotic behavior of rotational energies of rigid X2Y-type molecules

In this study the asymptotic behavior of rotational energies of simple rigid molecules of X₂Y-type is considered. This behavior is obtained using various forms of an effective rotational Hamiltonian. The results of calculations for highly excited rotational energies of the molecules H₂O and CH₂ are presented.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 9–12, January, 1990.     

The High-Resolution Fourier Transform Spectrum of Dideuterated Methane CH2D2in the Region between 1900 and 2400 cm

The infrared spectrum of doubly deuterated methane CH₂D₂has been recorded in the region from 1900 to 2400 cm⁻¹at almost Doppler-limited resolution by using two high-resolution Fourier transform spectrometers. The vibrational bands observed include 2ν₄, ν₄+ ν₇, 2ν₇, ν₂, ν₈, ν₄+ ν₉, and ν₇+ ν₉, which were analyzed by taking into account Coriolis and Fermi interactions among them and also those with ν₄+ ν₅, ν₃+ ν₇, and ν₅+ ν₇. Most of the centrifugal distortion constants were constrained to appropriate values, while the vibrational term value and three rotational constants in each of the seven excited states were adjusted along with Coriolis and Fermi interaction parameters by the least-squares analysis of the observed spectrum. The vibration–rotation interaction constants α_sthus determined for the ν₂and ν₈states were combined with those of other fundamental states already published to calculate the equilibrium C–H distance.     

Pairing vibrational and isospin rotational states in a particle number and isospin projected generator coordinate method

Pairing vibrational and isospin rotational states are described in different approximations based on particle number and isospin projected, proton-proton, neutron-neutron and proton-neutron pairing wave functions and on the generator coordinate method (GCM). The investigations are performed in models for which an exact group theoretical solution exists. It turns out that a particle number and isospin projection is essential to yield a good approximation to the ground state or isospin yrast state energies. For strong pairing correlations (pairing force constant equal to the single-particle level distance) isospin cranking (-ωT_x) yields with particle number projected pairing wave function also good agreement with the exact energies. GCM wave functions generated by particle number and isospin projected BCS functions with different amounts of pairing correlations yield for the lowest T = 0 and T = 2 states energies which are practically indistinguishable from the exact solutions. But even the second and third lowest energies of charge-symmetric states are still very reliable. Thus we conclude that also in realistic cases isospin rotational and pairing vibrational states may be described in the framework of the GCM method with isospin and particle number projected generating wave functions.     

(2 + 1) Resonance enhanced multiphoton ionization of hydrogen chloride in a pulsed supersonic jet: Vacuum wavenumbers of rotational lines with detailed band analysis for excited electronic states of HCl

A comprehensive study of the excited electronic states of HCl is reported. Using resonance enhanced multiphoton ionization ((2 + 1) REMPI) and time-of-flight mass spectrometry (TOFMS) over 120 band systems are analyzed. Supersonic jet techniques are used to prepare rotationally cold species for laser spectroscopy in the 77 000 to 96 000 cm⁻¹ region. At least 50 new electronic states are characterized as well as several features only tentatively assigned previously. A long vibrational progression consisting of 29 vibrational levels of the deeply bound V¹Σ⁺(0⁺) valence/ion-pair state is studied. We also extend the identification and analysis to high vibrational levels of low-lying Rydberg states. The assignments of [²Π_i] Rydberg state complexes are evaluated in terms of spin-orbit coupling and united-atom calculations. In several band systems, the spectra exhibit anomalous rotational line intensities and broadened linewidths which are consistent with predissociation. Multiphoton ionization with mass spectrometry permits the investigation of isotope effects as well as the appearance of fragment species associated with repulsive potential curves.     

Isotope shift of the rotational structure of the levels of flexural states in H2Ox molecules (x=16, 17, 18)

In the paper we obtain analytic relations that determine the isotope shift of the rotational levels of the (Ov₂O) states of H₂O^x molecules (x = 16, 17, 18). We give theoretical predictions of the rotational levels of the ground state of the molecules H₂O¹⁷ and H₂O¹⁸ with high values of the quantum numbers J and k_a.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 80–84, September, 1984.