Line Parameters for Ozone Hot Bands in the 3.3-μm Spectral Region

Line positions, intensities, and lower state energies have been calculated for eight hot bands of ¹⁶O₃ in the 3.3-μm spectral region. The results are based on spectroscopic parameters deduced in recent high-resolution laboratory studies and improved rotational energy levels of the (103), (004), and (310) vibrational states derived by refitting earlier data and experimental (004) energy levels from measurements of the 4ν₃ - ν₃ hot band. The good quality of the new parameters has been verified through comparisons of line-by-line simulations with high-resolution laboratory spectra. The present work and the results of our analyses of the main bands at 3.6 μm [Smith et al., J. Mol. Spectrosc.139, 171-181 (1990)] and 3.3 μm [Camy-Peyret et al., J. Mol. Spectrosc.141, 134-144 (1990)] provide a complete set of ozone spectroscopic line parameters covering the 3-μm region.     

Water line parameters for weak lines in the range 9000-12 700 cm

A total of 7923 transitions previously derived from long pathlength, Fourier transform spectra of pure water vapor (Schermaul et al., J. Mol. Spectrosc. 211 (2002) 169) have been refitted and reanalyzed using a newly calculated variational linelist. Of these, 6600 lines are weaker than 1 × 10⁻²⁴ cm/molecule, for which reliable intensities are obtained. These weak lines include 1082 lines, largely due to H₂¹⁶O, which have not been previously observed. A total of 7156 lines were assigned resulting in 329 new energy levels for H₂¹⁶O spread over 32 vibrational levels. Estimates are also given for the band origins of the (022), (140), and (051) vibrational states.     

Ab initio ro-vibrational Hamiltonian in irreducible tensor formalism: a method for computing energy levels from potential energy surfaces for symmetric-top molecules

A theoretical approach to study ro-vibrational molecular states from a full nuclear Hamiltonian expressed in terms of normal-mode irreducible tensor operators is presented for the first time. Each term of the Hamiltonian expansion can thus be cast in the tensor form in a systematic way using the formalism of ladder operators. Pyramidal XY₃ molecules appear to be good candidates to validate this approach which allows taking advantage of the symmetry properties when doubly degenerate vibrational modes are considered. Examples of applications will be given for PH₃ where variational calculations have been carried out from our recent potential energy surface [Nikitin et al., J. Chem. Phys. 130, 244312 (2009)].     

Spectrum of hot water in the 2000-4750 cm frequency range

An emission spectrum recorded in an oxyacetylene torch [P.-F. Coheur, P.F. Bernath, M. Carleer, R. Colin, O.L. Polyansky, N.F. Zobov, S.V. Shirin, R.J. Barber, J. Tennyson, J. Chem. Phys. 122 (2005) 074307] is analyzed for the region covering stretching fundamentals and associated hot bands of water. Many lines could be assigned on the basis of previously determined energy levels. New assignments made with a new variational linelist allow a further 800 energy levels covering 15 vibrational states and rotations up to J = 32 to be assigned. A simultaneous re-analysis of previously reported sunspot absorption spectra leads to the assignment of 581 further lines in the L-band spectrum and 67 in the N-band spectrum.     

Intracavity laser absorption spectroscopy of D2O between 11 400 and 11 900 cm

The weak absorption spectrum of dideuterated water, D₂O, has been recorded by Intracavity Laser Absorption Spectroscopy (ICLAS) between 11 400 and 11 900 cm⁻¹. This spectrum is dominated by the 3ν₁ + ν₂ + ν₃ and the ν₁ + ν₂ + 3ν₃ centered at 11 500.25 and 11 816.64 cm⁻¹, respectively. A total of 530 energy levels belonging to eight vibrational states were determined. The rovibrational assignment process of the 840 lines attributed to D₂O was mostly based on the results of new variational calculations consisting in a refinement of the potential energy surface of Shirin et al. [J. Chem. Phys., 120 (2004) 206] on the basis of recent experimental observations, and a dipole moment surface from Schwenke and Partridge [J. Chem. Phys. 113 (2000) 6592]. The overall agreement between these calculations and the observed spectrum is very good both for the line positions and the line intensities.     

Line frequency and line intensity analyses of water vapour

Line position and line intensity analyses of new microwave and infrared data pertaining to water and involving the ground and (010) vibrational states are carried out using the same theoretical approach as in Coudert, L. H., 1997, J. molec. Spectrosc., 181, 246. The line position analysis involves the high J and K_a lines measured by Polyansky, O. L., Zobov, N. F., Viti, S., Tennyson, J., Bernath, P. F. and Wallace, L., 1997, J. molec. Spectrosc., 186, 422 and the ν₂ band transitions published by Toth, R. A., 1998, J. molec. Spectrosc., 190, 379. In contrast to the previous investigation, the maximum K_a value in the data set is 24 for the ground vibrational state and 21 for the (010) state. The data set considered in the line intensity analysis includes mainly the line intensities reported by Toth and is much more complete than that fitted in the present author's previous investigation as it contains many lines within the ground and (010) vibrational states. The theoretical approach accounts correctly for the observed data for both analyses. However, in the line position analysis, a few transitions had to be excluded from the fitting because they involved high lying perturbed rotational levels belonging to the (010) vibrational state.     

Three-body interaction-induced light scattering in krypton gas: a computer simulation of the spectral line shapes

The two-, three- and four-body effective collision induced scattering spectral line shapes are calculated for dense gaseous krypton using the pairwise additivity (PA) approximation and different polarizability models. These spectra and several interaction induced spectra calculated at various densities are compared with the experimental measurements of Barocchi et al. [1988, Europhys. Lett., 5, 607]. The potential effect on the spectrum is found to be weak. The results obtained with the Meinander et al. [1986, J. chem. Phys., 84, 3005] empirical polarizability model and molecular dynamics fit well the experimental two- and three-body spectral shapes. The irreducible contribution to the spectral shape is evaluated using the dipole induced dipole irreducible polarizability [buckingham, A. D., and Hands, I. D., 1991, Chem. Phys. Lett., 185, 544]. This contribution is found to be relatively weak for the anisotropic spectra in the frequency and density range studied, explaining the good agreement between the pairwise approximation calculations and the experimental data. The spectra radiated by the quasi-molecules Kr₂, Kr₃, and Kr₄ (the total spectrum within the PA approximation) are also simulated.     

Fourier transform absorption spectra of H2O and H2O in the 8000-9400 cm spectral region

Fourier transform spectra of water vapor enriched in ¹⁸O and ¹⁷O were recorded between 8012 and 9336 cm⁻¹ and analyzed for the first time. High accuracy ab initio predictions of line positions and intensities by Partridge and Schwenke [J. Chem. Phys. 106 (1997) 4618-4639; 113 (2000) 6592-6597] were used in the process of spectrum assignment. Transitions involving the (031), (111), (130), (210), and (012) upper vibrational states were identified in the recorded spectra. As a result, 514 and 244 precise ro-vibrational energy levels were derived for the H₂¹⁸O and H₂¹⁷O molecules, respectively. High-order resonance perturbations between levels of the vibrational states involved were evidenced leading to the identification of a number of rotational levels of the (050) and (060) highly excited bending states.     

Water dimer vibration-rotation tunnelling levels from vibrationally averaged monomer wavefunctions

The vibration-rotation tunnelling (VRT) spectra for the water dimer obtained by vibrationally averaging the dimer potential over accurate water monomer wavefunctions is reported. The vibrational averaging requires evaluation of the 12D dimer potential energy surface at more than 10¹² distinct geometries. The resulting vibrational spectra of the low-lying dimer states are presented and compared with both less computationally expensive methods based on fixed nuclei approximations and the recent (6+6)d adiabatic calculations of Leforestier et al. [38] (2009). The procedure gives some modest improvement in the agreement with experimental values for the vibration-rotation tunnelling (VRT) states of (H₂O)₂ and (D₂O)₂. This approach can be extended to treat dimer states involving monomer overtone excitations, which is important in obtaining water dimer spectra at infrared and visible wavelengths at atmospheric temperatures, and in characterizing the dimer contribution to the so-called water continuum absorption at these wavelengths.     

Ro-vibrational spectra of C2H2 based on variational nuclear motion calculations

A published ab initio-based potential energy surface and newly constructed dipole moment surface of acetylene have been used to compute vibrational band intensities. The line intensity calculations employed the variational nuclear motion code WAVR4 for computation of wave functions and energy levels, and a newly developed code DIPOLE4 for computation of dipole transitions. Owing to the high computational cost of J > 0 transitions using direct variational methods only J = 0 and J = 1 states and transitions have been computed variationally. The intensities of J > 1 transitions were extrapolated from J = 0 and J = 1 using Hönl–London coefficients. The resulting effective rotational constants B and transition intensities are compared with experimental data for the (3ν₄ + ν₅) combination band, the ν₃ and the ν₅ fundamental band. The prospects of using this procedure for extensive calculations of a hot line list, important for cool stars and extrasolar planets are discussed.     

Influence of isotopic substitution on spectral and structural parameters of an isolated [F(HF)<Subscript>2</Subscript>]— complex. Substitution of a proton by a kaon and a triton

This paper continues the theoretical study (see V. P. Bulychev and M. V. Buturlimova, J. Mol. Struct. 928, 32 (2009)) of the isotopic effects in the H-bonded anionic complex [F(HF)₂]-. Isotopomers of the complex with significant differences between the masses of the light atoms are considered. The four-dimensional anharmonic vibrational problem are solved by the variational method for the symmetric complex [F(KaF)₂]-, in which both protons are substituted by a positive kaon (positive K-meson), and for the asymmetric complex [FKaFTF]-. Variables related to the changes in the lengths of molecular fragments LF (L = Ka and T) and the distances between the F^- anion and the centers of mass of LF are used as the vibra-tional coordinates. The potential energy surfaces are calculated in the MP2/6-311++G(3df,3pd) approximation taking into account the basis set superposition error. The vibrational energy levels, frequencies, and absolute intensities for spectral transitions are determined. To study the isotope effect on the geometrical parameters of the complex, the values of internuclear separations and the asymmetry parameter of the F^-…L-F bridge averaged over the ground state and several excited vibrational states are calculated, as well as their standard deviations. The calculated results are compared to the data obtained previously for the symmetric complexes [F(HF)₂]^-, [F(DF)₂]^-, and [F(TF)₂]^-.     

A refined potential energy surface and the rovibrational states for the electronic ground state of ozone

A potential energy surface for the electronic ground state of ozone has been optimized by using a variational procedure with the exact vibrational Hamiltonian in bond length-bond angle coordinates. In the optimization, the ab initio force field of Borowski, P., Andersson, K., Malmquist, P.-A., and Roos, B. O., 1992, J. chem. Phys., 97, 5568 is taken as the starting point, and the recent observed vibrational band origins up to 4900 cm^-1 reported by Floud, J.-M., Barbe, A., Camy-Peyret, C., and Plateaux, J. J., 1996, J. molec. Spectrosc., 177, 34 are involved. The root mean square error of this fit for the 39 observed vibrational energy levels is 0.83 cm^-1. In order to test the refined potential, the rovibrational energy levels up to J = 15 are calculated and compared with the observed values.     

Emission spectrum of hot HDO below 4000 cm

Fourier transform emission spectra were recorded using a mixture of H₂O and D₂O at a temperature of 1500 °C. The spectra were recorded in three overlapping sections and cover the wavenumber range 1800-3932 cm⁻¹. This spectrum is analyzed together with a previously reported one spanning the 380-2190 cm⁻¹ range [Parekunnel et al., J. Mol. Spectrosc. 2001 (28) 101]. This analysis leads to 4409 newly assigned HDO emission lines. This work particularly extends data on the (200) and (120) states of HDO for which newly determined energy levels are presented.     

The rovibrational levels of ammonia

In this paper we report variational rovibrational studies on ammonia and its isotopomers. We use six internal coordinates (one of which describes the umbrella motion). The expansion functions are products of one-dimensional functions of these internal coordinates, multiplied by appropriate functions of the Euler angles to describe the rotational motion. We use a previously published high accuracy six-dimensional potential energy surface [LEONARD, C., HANDY, N. C., CARTER, S., and BOWMAN, J. M., 2002, Spectrachim. Acta, 58, 825]. We derive the full kinetic energy operator for the rovibrational motion in these coordinates. This operator has been completely checked to give a hermitian secular matrix. All matrix elements are evaluated numerically by quadrature. The symmetry of the expansion functions is fully described in D_3h, C_2v and C_s. It is not possible to perform the calculations in D_3h, but complete degeneracy in the appropriate levels is obtained with the C_2v program. The algebraic complexity of this program has been far greater than for any other variational study we have undertaken for a tetra-atomic molecule.

We present J = 0, 1, 2 energy levels for the experimentally observed band origins of NH₃, and J = 0, 1 energy levels for the ground state and fundamentals of NH₂D, ND₂H and ND₃. For the asymmetric isotopomers, identical results are obtained for both C_2v and C_s, thus confirming the validity of the method. The levels we obtain are completely converged. Agreement with observation is of the order of 0.5% (of course being dependent upon the accuracy of the potential energy surface); therefore the ordering of the rotational levels and their splitting is completely predicted and understood.     

(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.     

Weak Line Water Vapor Spectrum in the 11 787-13 554 cm Region

Long-pathlength Fourier transform spectra of water vapor recorded previously by Schermaul et al. (J. Mole. Spectrosc.211, 169 (2002)) are analyzed in the range 11 787-13 554 cm⁻¹. Wavenumbers, absolute intensities, and self-broadening coefficients, with associated uncertainties, are presented for 2137 lines. Analysis of these lines using variational linelists has been conducted leading to the assignment of 1906 of the new lines to 23 different upper vibrational states in the 3ν+δ, 4ν, and 4ν+δ polyads, a further 19 lines are ascribed to H₂¹⁸O. Comparisons are made with the HITRAN database.     

Water vapour line assignments in the 9250-26 000 cm frequency range

Line parameters for water vapour in natural abundance have recently been determined for the 9250-13 000 cm⁻¹ region [M.-F. Mérienne, A. Jenouvrier, C. Hermans, A.C. Vandaele, M. Carleer, C. Clerbaux, P.-F. Coheur, R. Colin, S. Fally, M. Bach, J. Quant. Spectrosc. Radiat. Transfer 82 (2003) 99] and the 13 000-26 000 cm⁻¹ region [P.-F. Coheur, S. Fally, M. Carleer, C. Clerbaux, R. Colin, A. Jenouvrier, M.-F. Mérienne, C. Hermans, A.C. Vandaele, J. Quant. Spectrosc. Radiat. Transfer 74 (2002) 493] using a high-resolution Fourier-transform spectrometer with a long-path absorption cell. These spectra are analysed using several techniques including variational line lists and assignments made. In total, over 15 000 lines were assigned to transitions involving more than 150 exited vibrational states of H₂¹⁶O. Twelve new vibrational band origins are determined and estimates for a further 16 are presented.     

Rotation-vibration energy cluster formation in XH2D and XHD2 molecules (X = Bi, P, and Sb)

We investigate theoretically the energy cluster formation in highly excited rotational states of several pyramidal XH₂D and XHD₂ molecules (X = Bi, P, and Sb) by calculating, in a variational approach, the rotational energy levels in the vibrational ground states of these species for J?70. We show that at high J the calculated energy levels of the di-deuterated species XHD₂ exhibit distinct fourfold cluster patterns highly similar to those observed for H₂X molecules. We conclude from eigenfunction analysis that in the energy cluster states, the XHD₂ molecule rotates about a so-called localization axis which is approximately parallel to one of the X-D bonds. For the mono-deuterated XH₂D isotopologues, the rotational spectra are found to have a simple rigid-rotor structure with twofold clusters.     

Inelastic neutron scattering spectroscopy of C60@calix[8]arene

The vibrational dynamics of the p-rert-butylcalix[8]arene and the 1:1 inclusion complex C₆₀@p-tert-butylcalix[8]arene are investigated by a combination of inelastic neutron scattering (INS) and MM3 molecular mechanics calculations. The results show that the isolated, single molecule approximation breaks down and is not sufficient to explain the features observed experimentally. The origin of the line broadening in the low energy region is discussed in terms of intermolecular interactions: this effect is sharper in the case of the complex with the C₆₀ molecule, due to the high number of co-conformers allowed by the mismatch between the circumferences of the host and the guest. The successful interpretation of the INS spectra validates the use of the model adopted.     

First principles analysis of the MgAl2O4:Ni absorption spectrum

Analysis of the energy-level scheme and absorption spectrum of the Ni²⁺ ion in MgAl₂O₄ was performed. The recently developed first-principles approach to the analysis of the absorption spectra of impurity ions in crystals based on the discrete variational multi-electron (DV-ME) method [K. Ogasawara, et al., Phys. Rev. B 64 (2001) 115413) was used in the calculations. The method is based on the numerical solution of the Dirac equation; no phenomenological parameters are used in the calculations. As a result, complete energy-level scheme of Ni²⁺ and its absorption spectra were calculated, assigned and compared with experimental data on the ground and excited state absorption spectra. Numerical contributions of all possible electron configurations into the calculated energy states were determined. By performing analysis of the molecular orbitals population, numerical contributions of the oxygen 2p- and 2s-orbitals into the 3d molecular orbitals were determined.