Experimental study of the Na2 3Πg state

The 3¹Π_g state of Na₂ is experimentally investigated by using high resolution cw optical-optical double resonance spectroscopy. A single line Ar⁺ laser (total of 9 lines) is used to pump the sodium dimers from thermally populated ground state to the intermediate B¹Π_u state. Then a single mode Ti:sapphire laser is used to probe the 3¹Π_g state. Violet fluorescence from highly Rydberg excited states (mainly 2³Π_g or 3³Π_g states which are transferred from 3¹Π_g state via collisions) to the state is monitored by a filtered photomultiplier tube and a lock-in amplifier. Compared with previous studies [C.C. Tsai, J.T. Bahns, W.C. Stwalley, J. Chem. Phys. 99 (1993) 7417], a wider range of rotational quantum numbers of data field are observed. A set of Dunham coefficients and the Rydberg-Klein-Rees potential energy curve of the 3¹Π_g state are deduced from all the observed rovibrational levels.     

Fourier transform spectroscopy of chemiluminescence from the AΠ-XΣ system of SrO

The A^′1Π-X¹Σ⁺ near infrared system of strontium oxide (SrO) was observed at high spectral resolution by measuring the chemiluminescence from a Broida flow reactor using a Fourier transform spectrometer. In total, 32 bands from , , were measured within the spectral region at a resolution of . Vibrational levels of the upper state were observed up to v_A^′=4, and more than 5600 rotational lines were assigned. Incorporating previously published high resolution data for the A¹Σ⁺-X¹Σ⁺ system, a global fit to both data sets yields improved Dunham constants for the ground state and for the lower vibrational levels (v_A^′=0, 1, and 2) of the A^′1Π state. Because perturbations arising from interactions with the b³Σ⁺ and A¹Σ⁺ states affect the higher vibrational levels of the A^′1Π state more strongly, levels v_A^′=3 and 4 were represented by effective band constants in the fits. RKR potentials for the X¹Σ⁺,A^′1Π, and b³Σ⁺ states have been generated utilizing all the available data, Franck-Condon factors have been calculated for the A^′1Π-X¹Σ⁺ system, and A^′1Π∼b³Σ⁺ and A^′1Π∼A¹Σ⁺ perturbations are discussed.     

Optical emission spectroscopy of Ar-N2 mixture plasma

Optical emission spectroscopy measurements are presented to characterize the different excitation and ionization processes of both atomic and molecular species in Ar-N₂ mixture plasma under different discharge conditions. Particularly, the emission intensities of nitrogen (0-0) band of second positive system at 337.1 nm and (0-0) band of first negative systems at 391.4 nm are used to determine the dependence of their radiative states on argon fraction in the mixture. It is observed that the addition of argon gas influences the radiative states differently due to their different populating mechanisms. The results demonstrate that the addition of argon to nitrogen plasma remarkably enhance the population of N₂(C³Π_u) radiative state through Penning excitation involving argon metastable states. The electron temperature is determined from Ar-I spectral line intensities, using Boltzmann's plot method and is found to depend on argon fraction in the mixture.     

Stretch-bend combination polyads in the ÃAu state of acetylene, C2H2

Rotational analyses are reported for a number of newly-discovered vibrational levels of the S₁-trans (ùA_u) state of C₂H₂. These levels are combinations where the Franck-Condon active and vibrational modes are excited together with the low-lying bending vibrations, and . The structures of the bands are complicated by strong a- and b-axis Coriolis coupling, as well as Darling-Dennison resonance for those bands that involve overtones of the bending vibrations. The most interesting result is the strong anharmonicity in the combinations of (trans bend, a_g) and (in-plane cis bend, b_u). This anharmonicity presumably represents the approach of the molecule to the trans-cis isomerization barrier, where ab initio results have predicted the transition state to be half-linear, corresponding to simultaneous excitation of and . The anharmonicity also causes difficulty in the least squares fitting of some of the polyads, because the simple model of Coriolis coupling and Darling-Dennison resonance starts to break down. The effective Darling-Dennison parameter, K₄₄₆₆, is found to increase rapidly with excitation of , while many small centrifugal distortion terms have had to be included in the least squares fits in order to reproduce the rotational structure correctly. Fermi resonances become important where the K-structures of different polyads overlap, as happens with the 2¹3¹B¹ and 3¹B³ polyads (B = 4 or 6). The aim of this work is to establish the detailed vibrational level structure of the S₁-trans state in order to search for possible S₁-cis (¹A₂) levels. This work, along with results from other workers, identifies at least one K sub-level of every single vibrational level expected up to a vibrational energy of 3500 cm⁻¹.     

The overtone spectrum of carbonyl sulfide in the region of the ν1+4ν3 and 5ν3 bands by ICLAS-VECSEL

The high-resolution overtone spectrum of OCS has been recorded in the region of the ν₁+4ν₃ and 5ν₃ bands by intracavity laser absorption spectroscopy based on an optically pumped vertical external cavity surface emitting laser (VECSEL). The extremely weak ν₁+4ν₃ band at was found to be isolated. The 5ν₃ band at is accompanied by two weaker bands at 9933.53 and assigned to the 12⁰4-00⁰0 and 04⁰4-00⁰0 bands, respectively. In addition, the 01¹5-01¹0 hot band was detected together with the extremely weak band heads of the R branch of the 02^0,25-02^0,20 hot bands. Finally, the 5ν₃ band of the ¹⁶O¹²C³⁴S minor isotopomer, present in natural abundance in the sample, was also observed and rotationally analyzed. Effective state parameters could be retrieved by standard band-by-band rotational fitting of the line positions, leading to a typical rms of . The observed line positions were compared to the predictions of the global model described by Rhaibi et al. [J. Mol. Spectrosc. 191 (1998) 32-44]. In general, the agreement is excellent, close to the experimental uncertainty () thus confirming the high predictive ability of this effective Hamiltonian model. Weak but significant deviations up to were, however, identified for two rotational levels of the highly excited 2,16⁰,0 dark state, observed through a local interaction with the 00⁰5 state. In the case of the ¹⁶O¹²C³⁴S isotopomer, the predicted line wavenumbers of the 5ν₃ band were globally overestimated by about . The new data have been included in the corresponding global model, leading to almost unchanged values of the molecular parameters and a statistical agreement with the experiment.     

Microwave study of the rotational spectrum of oxygen molecule in the range up to 1.12 THz

Microwave study of the rotational transitions of oxygen molecule in its electronic and vibrational ground states is reported. Eight transitions belonging to N=3-1, N=5-3, and N=7-5 groups were investigated. Central line frequencies and pressure broadening parameters for O₂ and N₂ as perturbers were determined. The highest frequency of measured transition (N,J)=(7,6)-(5,6) has been 1.12 THz. Spectrometer with backward wave oscillator (BWO) and acoustic detector (RAD) was used. Since this experiment has more than doubled the number of previously measured rotational lines of oxygen molecule and better accuracy was achieved, the fitting of new set of rotational transition frequencies has been performed and new more accurate molecular constants for in , v=0 state have been obtained.     

Measurement of ultraweak transitions in the visible region of molecular oxygen

A highly sensitive cavity-enhanced frequency modulation spectroscopy technique has been used to measure ultraweak transitions in molecular oxygen that had not previously been characterized. The self-broadened half-width and line intensity of the measured transitions are reported. We include 12 high J transitions in the band of ¹⁶O₂ (the so-called A band), 59 transitions in the hot band of ¹⁶O₂, and 17 high J transitions in the band of ¹⁶O¹⁸O. Our measurements of line positions of the ¹⁶O¹⁸O transitions are used to determine improved molecular constants for the excited state of ¹⁶O¹⁸O.     

Rotational and vibrational structure in the 288 nm band system of the FeCl2 radical

The laser excitation spectrum of the 288 nm band system of FeCl₂, formed in a free-jet expansion, has been recorded at a rotational temperature of approximately 10 K. Vibronic transitions are observed from the ground state to two close-lying excited electronic states that differ in inversion (g, u) parity. Two extensive progressions in the symmetric stretching vibration have been identified, referred to as Progressions A and B. The main features of Progression A, which is based on the band, are allowed transitions to the excited electronic state of ungerade symmetry. Progression B is built on the band and consists of vibronically induced transitions to the gerade excited state. A substantial decrease in the symmetric stretching vibrational wavenumber is observed on excitation . Local perturbations are found to cause relative shifts between the different isotopomers. Several vibronic bands have been recorded and analysed at rotational resolution for the three isotopomers Fe³⁵Cl₂, Fe³⁵Cl³⁷Cl, and Fe³⁷Cl₂ in natural abundance. All bands show perpendicular rotational structure of a linear molecule, and have been unambiguously assigned to a Ω = 5-4 transition, consistent with the inverted ⁵Δ_g ground state predicted by ab initio and DFT calculations. The zero-point averaged FeCl bond length is determined to be in the upper and lower electronic states. The results show that the molecule is linear in both states.     

Structure and broadening coefficients (He, Ar and N2) of the ν4 band of CF4

Spectra of CF₄ in the ν₄ fundamental band region have been recorded in pure gas and in mixtures with He, Ar and N₂ at resolution up to . Obtained data allowed us to evaluate the integrated band intensity, line intensity distribution and effective broadening coefficients for J-multiplets. The broadening coefficient behavior is similar to that previously registered for linear molecules: they coincide for P and R branches; the J-dependence in the case of argon is more pronounced than that for helium. The broadening coefficients for nitrogen and helium are practically the same but the values for nitrogen are scattered around the general trend.Q-branch broadening is different from that for J-manifolds. The coefficients of branch broadening are noticeably smaller. Nitrogen broadening is very close to result for the case of argon though there is a marked difference between them for J-manifolds. Collisions with argon and nitrogen broaden the Q-branch almost 3 times more effectively than collisions with helium.     

Gas phase electronic spectrum of propadienylidene C3H2

The rotationally resolved vibronic bands in the forbidden electronic transition of the cumulene carbene C₃H₂ have been observed in the gas phase by cavity ring down absorption spectroscopy through a supersonic planar plasma with allene as precursor. The band detected in the 16 223 cm⁻¹ region is a result of vibronic interaction and is assigned to a combination of a₁ and b₂ vibrations with a frequency around 2250 cm⁻¹. Another vibronic band near 15 810 cm⁻¹ has an unusual rotational structure because the K_a = 0-1 subband is absent. It is assigned to a combination of a₁ and b₁ vibrations, ∼1850 cm⁻¹, which borrow intensity from the near lying state due to a-type Coriolis coupling. A rotational analysis using a conventional Hamiltonian for an asymmetric top molecule yields molecular constants for the vibrational excited levels of the ùA₂ state, which were used for the determination of the geometry. The stronger transition of C₃H₂, measured in a neon matrix in the 16 161-24 802 cm⁻¹ range, was not detected. The reason for this is a short lifetime of the state, leading to line broadening.     

Determination of line strengths for selected transitions in the v2 band relative to the v1 and v5 bands of H2CO

The spectral line strengths in the v₂ band of H₂CO (segments spanning 1720-) have been determined relative to two sets of spectral line groups in the v₁ and v₅ band, using tunable diode laser spectroscopy. Simultaneous detection using a dual-diode instrument with a absorption cell was employed to assure identical H₂CO column density for the two spectral regions. The results in the selected regions of this study are in good agreement with the line positions and the relative intensities specified in an unpublished complete line listing for the v₂ band prepared by Linda Brown (see full text for reference). Based upon measurements of individual groups of spectral lines in the P, Q and R branches, the absolute band strength has been determined to be .     

New analysis of the ν5+ν9−ν9 hot band of HNO3

Nitric acid which is an important NO_x atmospheric reservoir molecule exhibits a strong absorption in the spectral region. Since this region, which corresponds to an atmospheric window, is one of the most commonly used for the retrieval of HNO₃ in the atmosphere it is essential to have the best possible corresponding spectral parameters. Updates of these spectral line parameters were recently performed in the last versions of the atmospheric databases. They concern the line positions and intensities not only of the two interfering cold bands ν₅ and 2ν₉ but also of the ν₅+ν₉−ν₉ hot band. This hot band exhibits indeed a sharp and strong Q branch at which is clearly observable in atmospheric spectra and is used for the retrievals. However, in spite of these recent updates, it proved that the spectral parameters of the hot band are not accurate enough to reproduce accurately the observed atmospheric HNO₃ absorption in ATMOS spectra. The present paper is dedicated to a more accurate analysis of this hot band using new laboratory high-resolution (0.002-) Fourier transform spectra. As a consequence, new and more precise line positions and line intensities (about 35% weaker than in HITRAN2K) were derived leading to a significant improvement in the simulation of atmospheric spectra.     

High-resolution diode laser absorption spectroscopy of the O-H stretch overtone band (2,0,0)←(0,0,0) of the HO2 radical

The O-H stretching overtone (2ν₁) of the HO₂ radical was observed between 6603.2 to by using tunable diode laser absorption spectroscopy (TDLAS). About 1000 lines were observed in this region of which 491 transitions could be definitively assigned to the 2ν₁. The spectrum is observed to be an A/B hybrid band with band features of both a perpendicular and parallel nature. Transitions of the A-type bands with K_a^′=0-3, N^′?16 and transitions of the B-type bands with K_a^′=0,1, N^′?15 were assigned. The origin calculated from the best fit to the present spectrum is at which is ∼ higher than previously reported. The overtone spectrum is observed to be heavily perturbed, possibly by Fermi resonance with energy levels of the nearby (ν₂+5ν₃) state.     

The v6 = 1 and v6 = 2 vibrational states of DCF3

The high-resolution infrared spectra of DCF₃ were reinvestigated in the ν₆ fundamental band region near 500 cm⁻¹ and around 1000 cm⁻¹ with the aim to assign and analyze the overtone level of the asymmetric CF₃ bending vibration v₆ = 2.The present paper reports on the first study of both its sublevels (A₁ and E corresponding to l = 0 and ±2, respectively) through the high-resolution analysis of the overtone band and the hot and bands.The well-known “loop method”, applied to and , yielded ground state energy differences Δ(K, J) = E₀(K, J) − E₀(K − 3,J) for the range of K = 6 to 30.In the final fitting of molecular parameters, we used the strategy of fitting all upper state data together with the ground state rotational transitions.This is equivalent to that calculating separately the and coefficients of the K-dependent part of the ground state energy terms from the combination loops.All rotational constants of the ground state up to sextic order could be refined in the calculation.This led to a very accurate determination of C₀ = 0.18924413(25) cm⁻¹, , and also .In the course of analyzing simultaneously the overtone band together with the and ν₆ bands, the original assignment of the fundamental ν₆ band [Bürger et al., J. Mol. Spectrosc. 182 (1997) 34-49] was found to be incompatible with the present one. Assignments of the (k + 1, l₆ = +1)/(k − 1,l₆ = −1) levels had to be interchanged, which changed the value of Cζ₆ = −0.14198768(26) cm⁻¹ and the sign of the combination of constants C − B − Cζ in the v₆ = 1 level to a negative value.     

Σu and Πu states of the hydrogen molecule: Nonadiabatic couplings and vibrational levels

Nonadiabatic coupling matrix elements are computed for six lowest and four lowest ¹Π_u electronic states of H₂ in a wide range of internuclear distances. These matrix elements are used together with the adiabatic potentials to determine the bound ro-vibrational levels of the 10 electronic states for rotational quantum numbers J ? 10. The computed energies agree quite well with existing experimental term values. However, some of the experimental levels should be assigned differently.     

Sub-Doppler high-resolution excitation spectroscopy of the S1 ← S0 transition of dibenzofuran

Rotationally resolved ultrahigh-resolution fluorescence excitation spectra of the S₁ ← S₀ transition of dibenzofuran have been observed using the technique of crossing a collimated molecular beam and the single-mode UV laser beam. 3291 rotational lines of the band and 3047 rotational lines of the band have been assigned. The band has been found to be a b-type transition, in which the transition moment is along the twofold symmetry axis of this molecule, and only the ΔK_a = ± 1 transitions were observed. The excited state is identified to be the S₁¹A₁(ππ^∗) state. In contrast with this, the band has been found to be an a-type transition in which the transition moment is along the long axis in plane. It indicates that the intensity of this vibronic band arises from vibronic coupling with the S₂¹B₂(ππ^∗) state. We determined the accurate rotational constants and the molecule have been shown to be planar both in the ground and excited states.     

Time-resolved infrared diode laser spectroscopy of the ν1 (C-O stretch) band of the CoCO radical

Infrared spectrum of the cobalt carbonyl radical CoCO produced by the 193 nm excimer laser photolysis of cobalt tricarbonyl nitrosyl Co(CO)₃NO was observed by time-resolved diode laser spectroscopy. More than 600 lines were identified as belonging to the ν₁ (C-O stretch) fundamental band, consisting of the Ω=5/2 and 3/2 subbands, and the associated hot bands , , , and . The ²Δ_i electronic ground state of CoCO was experimentally confirmed. The ν₁ band origins are 1974.172582(93) cm⁻¹ and 1973.53178(14) cm⁻¹ for the Ω=5/2 and 3/2 subbands, respectively. The rotational constant in the ground state was determined as B₀=4427.146(50) MHz. The centrifugal distortion constant D₀=1.1243(68) kHz was obtained for the Ω=5/2 substate of the ground state. The equilibrium rotational constant B_e=4435.44(14) MHz was derived, together with the vibration-rotation interaction constants.     

Multispectrum fitting of line parameters for C2H2 in the 3.8-μm spectral region

Using FT spectra (Bruker IFS 120, unapodized FWHM resolution ≈ 0.001 cm⁻¹) of acetylene ¹²C₂H₂, absolute positions and intensities have been measured for about 250 lines between 2600 and 2800 cm⁻¹ in the and cold bands, and in the and hot bands. These measurements improve the accuracy of wavenumbers previously available and lead to individual line intensities for the first time in this spectral region. A multispectrum fitting procedure has been used to retrieve line parameters from five experimental spectra recorded at different pressures. The frequencies of the ν₃ band of ¹²C¹⁶O₂ allowed to perform an absolute wavenumber calibration. The accuracy of the amount of ¹²C₂H₂ in the sample has been checked using the cold band around 2100 cm⁻¹, and has been estimated to be around ±2%. The average absolute accuracy of the line parameters obtained in this work has then been estimated to be ±0.0002 cm⁻¹ for line positions, and ±5% for line intensities. For each studied band, the vibrational transition dipole moment squared value has been determined, as also empirical Herman-Wallis coefficients. A complete line list containing positions and intensities for the five strongest bands around 3.8 μm has been set up for atmospheric applications.