Infrared tunable diode laser spectroscopy of the Δv = 2 band of 7Li127I

The high-resolution infrared spectrum of the Δv = 2 transitions of ⁷LiI has been measured at temperatures near 1050 K. The observations include vibrational transitions ranging from 2-0 to 10-8. The data were fit to a set of Dunham potential constants complete through the a₆ term, from which the Dunham rovibrational constants were calculated. The band centers for the v = 1-0 and v = 2-0 transitions were determined to be 491.17398 ± 0.00026 cm⁻¹ and 976.73042 ± 0.00038 cm⁻¹, respectively.     

Infrared tunable diode laser spectra of lithium fluoride at high temperatures

At temperatures up to 1300 K the high resolution spectrum has been measured for the 1-0 through 7-6 vibrational transitions of ⁷LiF and the 1-0 through 8-7 vibrational transitions of ⁶LiF. These infrared ro-vibrational measurements have been combined with microwave measurements taken from the literature to obtain a set of ten Dunham potential constants that reproduce all the measurements for both isotopic species to within their experimental uncertainty. The band center for the v = 1-0 transition is 894.34104±0.00020 cm^?1 for ⁷LiF and 946.12074±0.00024 cm^?1 for ⁶LiF.     

Infrared spectrum of boron chloride (BCl)

The spectrum of the Δv = 1 band of BCl was measured between 828 and 870 cm^?1 with a tunable diode laser. The absorptions of the v = 1-0, 2-1, 3-2, and 4-3 transitions of BCl were observed in both a microwave discharge and a dc discharge through BCl₃. Spectra of ¹¹B³⁵Cl, ¹¹B³⁷Cl, ¹⁰B³⁵Cl, and ¹⁰B³⁷Cl were observed in natural abundance. A set of eight Dunham coefficients was determined by fitting the data for all observed isotopic species with the appropriate reduced mass factors. A BCl bond distance, r_e = 0.1715283(31) nm, was determined which agrees with the value derived from the electronic spectrum of BCl. The band center for the v = 1-0 transition of ¹¹B³⁵Cl is ν₀ = 829.4087(8) cm^?1.     

Infrared diode laser spectroscopy of the PO radical

Vibration-rotation transitions of the PO radical in the X²Π_r state have been observed by a tunable infrared diode laser spectrometer. The analysis of the observed spectra gave the molecular constants in the v = 1 state and the band origin to be B = 0.7250107(36), D = 1.0253(60) × 10^?4, A_J = 0.997(24) × 10^?4, p = 0.006323(33), A₁ - A₀ = 0.16354(78), and ν₀ = 1220.24901(43), all in cm^?1 units with three standard errors in parentheses, where the v = 0 parameters were fixed to the values previously reported. The equilibrium internuclear distance was determined to be $\text{r}{}_{\mathrm{<mtext>e</mtext>}}\text{= 1.476370(15)}\text{A}\text{?}$.     

The infrared spectra of 12C32S, 12C34S, 13C32S,and 12C33S

Using a tunable diode laser spectrometer, the infrared absorption spectra of four isotopic species of carbon monosulfide have been observed in the positive column of a dc discharge of CS₂ and Ar. The wavenumbers of 115 vibration-rotation transitions between 1180.5 and 1266.1 cm^?1 have been measured. These lines were assigned to the 1-0, 2-1, 3-2, and 4-3 bands of ¹²C³²S, the 1-0 and 2-1 bands of ¹²C³⁴S and ¹³C³²S, and the 1-0 band of ¹²C³³S. These new data have been combined with the previous infrared and microwave results to determine Dunham coefficients (Y_ij), the Dunham potential expansion constants (a₀,a₁,a₂,a₃, and a₄), and the classical turning points by the RKR method.     

High-resolution spectroscopy of the v2 = 2 a ← v2 = 1 s band of 14NH3

Twenty-one transitions of the v₂ = 2 a ← v₂ = 1 s hot band of ¹⁴NH₃ have been observed by an infrared microwave sideband laser spectrometer with an absolute accuracy of 0.00002 cm⁻¹. One hundred and seventeen transitions of the band have been obtained by a Fourier transform infrared spectrometer at a resolution of 0.005 cm⁻¹. A weighted least-squares analysis of these data has been carried out to yield 17 molecular parameters for the v₂ = 2 a state. These parameters reproduce the experimental frequencies with a root mean square deviation of 0.000123 cm⁻¹. To calculate the frequencies to this accuracy it was necessary to take into account the Δ(K − l) = ±3 interaction between the v₂ = 2 a and v₄ = 1 a states.     

The vibrational numbering and improved constants of the A3Π1u state of I2

The A-X system of I₂ has been recorded in absorption, under conditions of medium resolution, over the region 8000 – 13 400 Å. Bandheads in progressions based on v″ = 6 through 18 have been measured and assigned. A new vibrational numbering for the A state is proposed, which leads to more reliable values for the important constants of the A state: T_e = 10 906 ± 3 cm^?1, D_e = 1641 ± 3 cm^?1, ω_e = 92.5 ± 0.5 cm^?1, ω_ex_e = 1.20 ± 0.08 cm^?1, ω_ey_e = ?0.062 ± 0.006 cm^?1.     

High-resolution spectroscopy of the v2 = 2 a ← v2 = 1 s band of 15NH3

Twenty-four transitions of the v₂ = 2 a ← v₂ = 1 s hot band of ¹⁵NH₃ have been observed by an infrared microwave sideband laser spectrometer. In addition, 149 transitions of the band have been obtained by a Fourier transform spectrometer at a resolution of 0.02 cm⁻¹. A weighted least-squares analysis has been carried out and the rms deviation of the fit is 0.00097 cm⁻¹. It was necessary to include the Δ(K − l) = ±3 interaction between the v₂ = 2 a and the v₄ = a states in the analysis.     

High-resolution infrared spectrum of the fundamental band of LiCl at a temperature of 830°C

High-resolution Fourier transform spectra of ⁶LiCl and ⁷LiCl have been recorded at 830°C. A total of 2522 lines have been measured at 0.006 cm⁻¹ resolution in the 500- to 730-cm⁻¹ region. The data for all four isotopic species have been fit with a standard deviation of 0.00027 cm⁻¹ using 19 isotopically invariant rovibrational constants including five Δ_ij correction terms to the usual Dunham Y_ij terms. Comparison is made with the constants derived from a direct fit of the observed transitions to a Dunham potential function with only 13 coefficients including for Δ correction terms. The gas phase band center for the v = 1–0 transition of ⁷Li³⁵Cl is 634.0753(7) cm⁻¹.     

Extension of the rotational analysis of the 1Π-X1Σ+ system of AsN

Rotational analysis of bands with v′ = 0 through 3, in the ¹Π-X¹Σ⁺ system as the AsN molecule, has been carried out. Rotational constants for the X¹Σ⁺ state are: B_e = 0.54551 cm^?1, α_e = 0.003366 cm^?1 and D_e = 5.3 × 10^?7cm^?1. Strong perturbations are observed in the upper levels and the resulting B_v curves are plotted against J.     

The 2880-Å emission spectrum of I2: Ion-pair states near 47 000 cm−1

An emission system of I₂ in Ar in the region 2830–2890 Å is examined under high resolution and found to display fine violet-degraded band structure. This system is interpreted as a charge-transfer transition originating from an ion-pair state near 47 000 cm^?1 and terminating on a weakly bound state which dissociates to two ground-state atoms. This interpretation is supported by spectral simulations employing a bound-free model. The transition is tentatively assigned as $\text{0}{}_{\mathrm{<mtext>g</mtext>}}{}^{\mathrm{?}}\text{→ 2431 0}{}_{\mathrm{<mtext>u</mtext>}}{}^{\mathrm{?}}\text{(}{}^3\text{Π}\text{)}$, according to which the excited state becomes the fourth ion-pair state near 47 000 cm^?1 to be experimentally characterized, and the lower state is the last component of the lowest ³Π state to be identified. The vibrational assignments include about 45 bands in ¹²⁷I₂ and ¹²⁹I₂, spanning v′ = 0–4 and v″ = 6–19, but with the numbering of the lower state remaining uncertain by several units. The main spectroscopic constants for the excited state are T_e = 47 070 cm^?1, ?_e = 105.7 cm^?1, ?_ex_e = 0.49 cm^?1. The spectral simulations place the lower state's potential curve 34 650 cm^?1 below the upper state at R = R′_e, with slope ?850 cm^?1/Å. For our “best” numbering of the lower state, ?_e = 20.5 cm^?1, ?_ex_e = 0.29 cm^?1, T_e = 12 190 cm^?1, and D_e = 360 cm^?1.     

High-resolution Fourier spectrometry of 14N2 and 15N2 infrared emission spectrum: Extensive analysis of the W3Δu - B3Πg system

The infrared spectrum of the nitrogen molecule, excited in a microwave discharge, has been recorded in high resolution by Fourier spectrometry in the range 2500–15 000 cm^?1. The precision of the measurements is estimated to be about 0.003 cm^?1. We have analyzed 19 bands of the W³Δ_u-B³Π_g system of ¹⁴N₂, with 0 ≤ v′ ≤ 7, and three bands of ¹⁵N₂ lying between 2500 and 5900 cm^?1. The molecular constants of the ³Δ_u and B³Π_g states have been determined by direct approach using an iterative nonlinear least-squares procedure. It has proved convenient to describe the levels of W³Δ_u state in a case a basis although in fact they approximate those of Hund's case b. Derived values of equilibrium constants of W³Δ_u are, in cm^?1: T_e = 8875.3347 (with origin taken in A, ³Σ_u⁺v = 0 level); ω_e = 1506.4859; ω_eχ_e = 12.5469; B_e = 1.4702537; α_B = 0.0170389; D_e = 0.55958 × 10^?5. RKR potential energy curves for the two states are constructed, and the Franck-Condon factors calculated for the W-B system.     

Analysis of the ν6 band of 12CH3D at 8.6 μm

The ν₆(E) fundamental vibration-rotation band of monodeuteromethane (¹²CH₃D) has been recorded in the spectral range 1033–1270 cm^?1 with a resolution of approximately 0.04 cm^?1. Of the 669 transitions with J′ ≤ 17 identified, 633 have been retained for the determination of the rotational levels in the upper state v₆ = 1. The Coriolis interaction between the v₆ = 1(E) and v₃ = 1 (A₁) vibrational states of ¹²CH₃D results in large A₁A₂ splittings of levels with v₆ = 1 and |K ? l₆| = 0 or 3; the mixing in K and l₆ also gives rise to some ten forbidden transitions observed in the spectra. These effects have been very well explained within the formulation based on the contact transformation method. Values of 15 molecular structure constants of the v₆ = 1 state have been determined from a least-squares analysis of the 633 retained transitions. These constants can be used to estimate values of the upper-state energies up to fourth order, and through them the spectral positions of the 633 retained transitions are reproduced with an overall standard deviation of 0.013 cm^?1, which is within experimental uncertainties.     

Observation of the v = 1 ← 0 band of SH (X2Π) with a difference frequency laser

The fundamental vibration-rotation band of SH (X²Π) has been studied in absorption at Doppler-limited resolution with an estimated accuracy of 0.002 cm^?1. The band origin (ν₀ = 2598.7675 ± 0.0003 cm^?1) and the molecular constants for the excited vibrational state (v = 1), as well as improved molecular constants for the ground vibrational state, have been determined in a least-squares fit.     

Vibration-rotation spectra of ethane and deuteroethanes: The ν2 band of CH3CD3

The ν₂ band of CH₃CD₃ has been measured under an effective resolution of 0.04 cm^?1. About 400 transitions observed in the region from 2130 to 2060 cm^?1 have been identified as due to the ν₂ fundamental band. The least-squares analysis of these transitions yields the band constants: ν₀ = 2089.957, B′ = 0.548937, D_J′ = 6.97 × 10^?7, D_JK′ = 1.92 × 10^?6, A′ - A″ = ?0.01158, and D_K′ - D_K″ = 1.30 × 10^?6 cm^?1. The ground-state constants B″, D_J″, and D_JK″ are fixed to the values obtained from microwave spectroscopy.     

Identification of matrix-isolated thorium nitride and the thorium-dinitrogen complex

The infrared stretching frequencies of Th¹⁴N and Th¹⁵N in solid Ar and Kr at 14 K have been measured. Multiple sites for the ThN in both matrices were observed; one site for Th¹⁴N with $\text{v}\text{?}\text{= 934.61 ± 0.05}\text{cm}{}^{\mathrm{?}}$ predominated after the matrix was annealed. For ThN in this site, ω_e = 941.9 ± 1.0 and ω_eχ_e = 3.7 ± 0.5 cm^?1. No dinitride of Th was observed. A thorium-dinitrogen complex was observed with a NN stretching frequency of 1828.59 ± 0.05 cm^?1 in solid Ar. The geometry of this complex is C_2v with equivalent nitrogen atoms and the bonding approaches that of an ion pair.     

The E → B transition (3000–3140 Å) in Br2

The region 3030–3140 Å of the emission spectrum of Br₂ is reinvestigated using sources containing separated ⁷⁹Br₂ and ⁸¹Br₂. The analysis, which spans v′ levels 0–15 and v″ levels 8–31, indicates that the transition in this region is the analog of the E → B system in I₂, and it is so redesignated. The following spectroscopic constants are obtained for the E state of ⁷⁹Br₂: T_e = 49 779.06 cm^?1, ω_e = 150.46 cm^?1, ω_eχ_e = 0.383 cm^?1, B_e = 0.04172 cm^?1, $\text{R}{}_{\mathrm{e}}\text{= 3.20}\text{A}\text{?}$.     

Dunham coefficients for seven isotopic species of CO

An extensive work on vibration-rotation spectra in the fundamental ¹Σ⁺ electronic state of CO is reported. More than 30 000 Doppler-limited measurements corresponding to about 8500 transitions of 255 bands of ¹²C¹⁶O, ¹²C¹⁸O, ¹³C¹⁶O, and ¹³C¹⁸O, most of them observed for the first time, have been obtained with a high information Fourier transform interferometer on the sequences Δv = 1, 2, and 3. The highest v and J values are 41 and 93, respectively. Experimental vibrational levels are then well observed up to three fourths of the dissociation energy limit. These accurate infrared wavenumbers, with an additional selected set of all previous measurements, have been simultaneously fitted to the Dunham expression in a weighted nonlinear least-squares calculation covering seven different isotopic species. It significantly improves both the number of parameters (U and Δ) obtained by the best previous work (35 instead of 23) and their corresponding standard deviations. The rms of the fit is equal to 13 × 10^?6 cm^?1 (390 KHz). Calculated wavenumbers from the 35 reduced Dunham and mass-scaling coefficients can then be used as secondary standards, even for transitions involving high v and J values of the various isotopic species. These new parameters should be a convenient and useful tool for several purposes, such as assignment of infrared laser lines and identification of microwave and infrared transitions in astronomical spectra. The Dunham coefficients Y are also reported for ¹²C¹⁶O, ¹²C¹⁷O, ¹²C¹⁸O, ¹³C¹⁶O, ¹³C¹⁷O, ¹³C¹⁸O, and ¹⁴C¹⁶O. These experimentally determined accurate Y should also be useful for further examination of the potential energy and dipole moment formulations.     

The ν2 and ν4 bands of AsH3

The infrared absorption of arsine, AsH₃, between 750 and 1200 cm^?1 has been recorded at a resolution of 0.006 cm^?1. Altogether 2419 transitions, including nearly 700 “perturbation allowed” transitions with Δ∥k ? l∥ = ±3, ±6, and ±9, have been assigned to the ν₂(A₁) and ν₄(E) bands. Splitting of the transitions for K″ = 3, 6, and 9 was also observed. To fit the rotational pattern of the v₂ = 1 and v₄ = 1 vibrational states up to J = 21, all the experimental data were analyzed simultaneously on the basis of a rovibrational Hamiltonian which took into account the Coriolis interaction between ν₂ and ν₄ and also included several essential resonances within them. The derived set of 38 significant spectroscopic parameters reproduced the 2328 transition wavenumbers retained in the final fit within the accuracy of the experimental measurements.     

Line strengths,spin-splittings,and forbidden transitions in the (101) band of 14N16O2

Measurements of line strengths in the (101) and (111)-(010) bands of ¹⁴N¹⁶O₂ have been made at a resolution of 0.02 cm^?1 in the region 2863 to 2934 cm^?1. The strength data in the (101) band were analyzed to determine a vibrational band strength and coefficients of the F factor. Each subband for K_?1 ≤ 9 was analyzed separately and all the F-factor coefficients in terms of the rotational quantum number, N, were found to be too small to be of significance. However, F was found to be dependent on K_?1 and the experimentally determined subband strengths were least-squares fitted to the expression S_v⁰·F, where S_v⁰ = 68.3 cm^?2 atm^?1 at 296 K and F = 1 + (2.899 × 10^?3)K_?1 + (4.08 × 10^?3)K_?1² ? (2.34 × 10^?4)K_?1³. The integrated strengths for the (101) and (111)-(010) bands were found to be 70.9 ± 2.3 and 2.7 ± 0.3 cm^?2 atm^?1 at 296 K, respectively. Also included in this study are measurements of line center positions in the two bands and spin-splittings in the (101) band. Recent frequency measurements of lines with K_?1 ≤ 8 in the (101) band have been made at a resolution of 0.0033 cm^?1 by V. Dana and J. P. Maillard (J. Mol. Spectrosc.71, 1–4) (1978)) for the region above 2889 cm^?1 and our values are in excellent agreement with theirs. Separations of the split lines measured in this work (K_?1 ≤ 10) agree well with calculated values using expressions which include the η_aaaaK_?1⁴ term with η′_aaaa = ?1.70 ± 0.15 × 10^?4 cm^?1 as derived for the (101) state. Three forbidden (ΔN ≠ ΔJ, ΔK_?1 = 0) transitions in the (101) band were observed with their identifications based on the agreement between measured and calculated line positions and strengths.