Analysis of the High-Resolution Infrared Spectrum of the PHD2 Molecule: ν1 and 2ν1 Bands

The results of investigation into the infrared spectra of the PHD₂ molecule including the ₁ fundamental band centered at 2324.005 cm^–1 (with a resolution of 4.2·10^–3 cm^–1) and the first 2₁ valence overtone centered at 4563.634 cm^–1 (with a resolution of 8.8·10^–3 cm^–1) are given in the present paper. Based on an analysis of the results obtained, 1340 and 1020 lines are referred to the ₁ and 2₁ bands, respectively. This data are used to calculate 316 and 248 vibrational-rotational energies of the (100000) and (200000) excited vibrational states, respectively. Since both bands can be considered as isolated, we take advantage of the Watson Hamiltonian (the reduction A in the I ^r representation) to describe their rotational structure. The calculated spectroscopic parameters of the examined states of the PHD₂ molecule correlate well with each other and with the corresponding parameters of the ground vibrational state.     

Line intensities in the ν1 + 2ν2, 2ν2 + ν3, 2ν1, ν1 + ν3, 2ν3, and ν1 + ν2 + ν3 − ν2 bands of H216O,between 6300 and 7900 cm−1

Using Fourier transform spectra, the intensities of 428 weak lines belonging to the ν₁ + 2ν₂, 2ν₂ + ν₃, 2ν₁, ν₁ + ν₃, 2ν₃, and ν₁ + ν₂ + ν₃ − ν₂ bands of the H₂¹⁶O molecule have been measured, between 6300 and 7900 cm⁻¹, with an average uncertainty of 7%.     

Study of the High-Resolution Fourier Spectrum of the ν9 and ν2 + ν7 + ν8 Bands of the С2D4 Molecule

Russian Physics Journal - Fourier spectra of the C2D4 molecule in the region 2250–3040 cm–1, in which the fundamental ν9 band and the combinational ν2 + ν7 + ν8 band...     

Line intensities for the ν1, ν3 and ν1+ν3 bands of 34SO2

Using both high resolution (0.0018 cm^?1) and medium resolution (0.112 cm^?1) Fourier transform spectra of an enriched ³⁴S (95.3%) sample of sulfur dioxide, it has been possible to accurately measure a large number of individual line intensities for some of the strongest of the SO₂ bands, i.e. ν₁, ν₃ and ν₁₊ν₃. These intensities were least-squares fitted using a theoretical model which takes into account the vibration–rotation interactions linking the upper energy levels where needed, and, in this way, expansions of the various transition moment operators were determined. The Hamiltonian parameters determined in previous analyses together with these moments were then used to generate synthetic spectra for the bands studied and their corresponding hot bands providing one with an extensive picture of the absorption spectrum of ³⁴SO₂ in the spectral domains, 8.7, 7.4, and 4 μm.     

Analysis of the Ro-Vibrational Structure of the Fundamental Band ν6 of 13CHF3 Molecule

Optics and Spectroscopy - The high-resolution IR spectrum of the fundamental band ν6 of 13CHF3 molecule, located in the region of 450–750 cm–1, has been investigated. The spectrum...     

Study of the ν2 + ν10 Hybrid Band of the Trans-C2H2D2 Molecule

Russian Physics Journal - The ν2 + ν10 (Bu) hybrid band of the trans-C2H2D2 molecule in the region 2100–2300 cm–1 is studied for the first time. The spectrum has been analyzed...     

The 2ν1 + ν3 and 3ν3 bands of 14N16O2

The spectra of the 2ν₁ + ν₃ and 3ν₃ bands of ¹⁴N¹⁶O₂ have been recorded by means of high-resolution Fourier transform spectroscopy and have been extensively analyzed. The (2 0 1) and (0 0 3) rotational levels deduced from the analysis have been reproduced within the experimental uncertainty using a Hamiltonian which takes into account the Coriolis interaction coupling the vibrational states of the diads {(2 2 0), (2 0 1)} and {(0 2 2), (0 0 3)}. Finally, precise sets of vibrational energies, and spin-rotation, rotational, and coupling constants have been derived for these vibrational states.     

High resolution vibration-rotation spectrum of the D2O molecule in the region near the 2ν1 + ν2 + ν3 absorption band

The high resolution Fourier transform spectrum of the D₂0 (ν = ν₁ + ν₂/2 + ν₃ = 3.5) polyad was analysed within the framework of the Hamiltonian model taking into account resonance interactions between the seven states (310), (211), (112), (013), (230), (131) and (032). Transitions belonging to the 2ν₁ + ν₂ + ν₃, 3ν₁ +ν₂ and 3ν₂ + 2ν₃ bands were assigned in the experimentally recorded spectrum. This provided the possibility of obtaining spectroscopic parameters of the ‘visible’ states (211), (310) and (032) and of estimating the band centres, and the rotational and resonance interaction parameters of the ‘dark’ states (112) and (131).     

Analysis of the stimulated Raman spectrum of the ν16ν2 + ν18 Fermi dyad of benzene

Ionization-detected stimulated Raman spectroscopy was used to obtain high-resolution recordings of the two perpendicular bands of the benzene molecule centered at 1591.327 and 1609.518 cm⁻¹. The effective resolution was further enhanced by deconvolving the spectrum to a linewidth 0.003 to 0.004 cm⁻¹. Fine-tuning of the ionizing radiation made it possible to record the transitions belonging to each band separately, thus greatly simplifying the spectrum in the region of overlap. The strong ^sS and ^oO branches were, for the most part, completely resolved as were many lines in the weaker ^oP and ^sR branches and even in the central ^oQ and ^sQ branches. The observed bands belong to the E_2g fundamental ν₁₆ in nearly exact Fermi resonance with the combination ν₂ + ν₁₈. A detailed rovibrational analysis of the spectrum is reported. A perturbation detected in the ^sS_k branches of the lower-frequency band for K = 19 to 23 was identified as a quintic anharmonic resonance with the third overtone, 4ν₂₀, of the lowest lying fundamental ν₂₀, which is infrared- and Raman-inactive (species E_2u). Deperturbed spectroscopic constants for the interacting states are reported which reproduce the observed line positions with a standard deviation of 0.0013 cm⁻¹. The unperturbed origins of the ν₁₆ and ν₂ + ν₁₈ states are only 1.106 cm⁻¹ apart. The fundamental ν₁₆ was identified with the higher-frequency state with origin at 1600.976 cm⁻¹.     

Measurements of the line strengths,N2− and O2-broadened half-widths in the ν3, ν1+2ν2 and 2ν1 bands of 14N2 16O at room temperature

The line strengths, N₂? and O₂-broadened half-widths in the ν₃, ν₁+2ν₂ and 2ν₁ bands of ¹⁴N₂ ¹⁶O were determined from spectra obtained by a high-resolution Fourier transform spectrometer at room temperature. The squared vibrational transition dipole moments and the coefficients of the Herman–Wallis factor were also determined for these bands. The squared vibrational transition dipole moments for these bands agreed with the values of HITRAN and high-resolution experiments within 6%. The N₂? and O₂-broadened half-widths were in agreement with the results of recent high-resolution experiments. The air-broadened half-widths were calculated using the smoothed N₂? and O₂-broadened half-widths and compared with the compiled values in the HITRAN database.     

High-Resolution Spectra of the ν2 + ν4 (F1,F2) and 2ν4 (F2) Bands of Deuterated Silane 28SiD4

Optics and Spectroscopy - The high-resolution spectrum of the 28SiD4 molecule in the range of 1260–1480 cm–1 is experimentally recorded, and the ν2 + ν4 (F1, F2) and 2ν4...     

On the Study of Resonance Interactions and Splittings in the PH3 Molecule: ν1, ν3, ν2+ν4, and 2ν4 Bands

The high-resolution (0.005 cm⁻¹) Fourier transform infrared spectrum of PH₃ is recorded and analyzed in the region of the fundamental stretching bands, ν₁ and ν₃. The ν₂+ν₄ and 2ν₄ bands are taken into account also. Experimental transitions are assigned to the ν₁, ν₃, ν₂+ν₄, and 2ν₄ bands with the maximum value of quantum number J equal to 15, 15, 13, and 15, respectively. a₁-a₂ splittings are observed and described up to the value of quantum number K equal to 10. The analysis of a₁/a₂ splittings is fulfilled with a Hamiltonian model which takes into account numerous resonance interactions among all the upper vibrational states.     

Study of the Rotational Structure of the Forbidden ν8 Band of the C2H2D2-CIS Molecule

Russian Physics Journal - The spectrum of the cis-ethylene-d2 (C2H2D2-cis) molecule is recorded with a Bruker IFS 120 HR Fourier spectrometer in the region of 600–1200 cm–1 with...     

High-resolution spectroscopy of difference and combination bands of SF6 to elucidate the ν3 + ν1 − ν1 and ν3 + ν2 − ν2 hot band structures in the ν3 region

The strong infrared absorption in the ν₃ S–F stretching region of sulphur hexafluoride (SF₆) near 948 cm^?1 makes it a powerful greenhouse gas. Although its present concentration in the atmosphere is very low, it is increasing rapidly, due to industrial pollution. The ground state population of this heavy species is only 32% at room temperature and thus many hot bands are present. Consequently, a reliable remote-sensing spectroscopic detection and monitoring of this species require an accurate modelling of these hot bands. We used two experimental set-ups at the SOLEIL French synchrotron facility to record some difference and combination bands of SF₆: (1) a new cryogenic multiple pass cell with 93 m optical path length and regulated at 163 ± 2 K temperature and (2) the Jet-AILES supersonic expansion set-up. With this, we could obtain high-resolution absorption spectra of the ν₃ ? ν₁, ν₃ ? ν₂, ν₁ + ν₃ and ν₂ + ν₃ bands at low temperature. These spectra could be assigned and analysed, thanks to the SPVIEW and XTDS computer programs developed in Dijon. We performed two global fits of effective Hamiltonian parameters. The first one is a global fit of the ground state, ν₂, ν₃, ν₃ ? ν₂, ν₂ + ν₃, 2ν₃ and 2ν₃ ? ν₃ rovibrational parameters, using the present spectra and previous infrared, Raman and two-photon absorption data. This allows a consistent refinement of the effective Hamiltonian parameters for all the implied vibrational levels and a new simulation of the 2ν₃ + ν₂ ? ν₂ hot band. The second global fit involves the present ν₃ ? ν₁ and ν₁ + ν₃ lines, together with previous ν₁ Raman data, in order to obtain refined ν₁ parameters and also ν₁ + ν₃ parameters in a consistent way. This allows to simulate the ν₃ + ν₁ ? ν₁ hot band.     

High-resolution investigation of the weak ν1+3ν21-ν21+ν3 band of CO2 around 2 μm

Fundamental spectroscopical parameters of the weak ν₁+3ν₂ ¹-ν₂ ¹+ν₃ band of CO₂ are reported using a high-resolution, direct-absorption spectrometer, based on a distributed feed-back diode laser emitting at 2 μm. Line intensities and self-broadening coefficients have been measured for the first time with high accuracy, for nine lines of the R branch, from R(44) up to R(59). Comparison with available data has been made, and a generally good agreement has been found. Received: 30 August 1999 / Published online: 24 March 2000     

First high-resolution analysis of the ν1, ν3 and ν1 + ν3 bands of sulphur dioxide 33S16O2

• High-resolution spectra of ³³S¹⁶O₂ have been recorded for the first time in the 8 and 4 µm spectral regions.

• The ν₁, ν₃ and ν₁ + ν₃ bands of the ³³S¹⁶O₂ have been analysed up to very high quantum numbers.

• Accurate ro-vibrational upper states constants have been determined.

     

Measurements and calculations of H2-broadening and shift parameters of water vapour transitions of the ν1 + ν2 + ν3 band

The water vapour line broadening and shifting for 97 lines in the ν₁ + ν₂ + ν₃ band induced by hydrogen pressure are measured with Bruker IFS 125 HR FTIR spectrometer. The measurements were performed at room temperature, at the spectral resolution of 0.01 cm^?1 and in a wide pressure range of H₂. The calculations of the broadening γ and shift δ coefficients were performed in the semi-classical method framework with use of an effective vibrationally depended interaction potential. Two potential parameters were optimised to improve the quality of calculations. Good agreements with measured broadening coefficients were achieved. The comparison of calculated broadening coefficients γ with the previous measurements is discussed. The analytical expressions that reproduce these coefficients for rotational, ν₂, ν₁, and ν₃ vibrational bands are presented.     

High resolution FTIR spectra and analysis of the ν11 fundamental and of the ν2 + ν11, ν5 + ν12 and ν7 + ν16 combination bands of 12C6D6

We report results from measurements of the high resolution FTIR spectrum for the fully deuterated benzene molecule C₆D₆ in the range 450–3500 cm^?1. Accurate spectroscopic constants have been obtained for the fundamental vibration ν₁₁ at 496.208 cm^?1 and improved ground state constants have been deduced from a fit of ground state combination differences. The J structure of the combination parallel bands ν₂ + ν₁₁ (at 2798.1 cm^?1), ν₅ + ν₁₂ (1802.5 cm_?1) and ν₇, + ν₁₆ (2619.3 cm^?1) of C₆D₆ has been analysed as well, from which improved values of the band origin and of the B and D _j constants of the excited states have been obtained. The strongest hot bands accompanying these parallel transitions have been assigned by means of the anharmonic force field calculated by Maslen et al. [1992, J. chem. Phys., 97, 4233]. In particular (ν₁₁ + ν₁₆) ? ν₁₆ is assigned to the band at 492.4 cm^?1 even though its shape is typical of a perpendicular transition (PAPE). New values for the ν₅, ν₁₂ and ν₁₆ band origins are determined from the band origins of combination bands and from calculated anharmonic constants. Numerous anharmonic constants are derived from the assignment of hot band and combination transitions.