High-resolution laser spectroscopy of CaNH2: Analysis of the C̃2A1-X̃2A1 system

Laser excitation spectra of the $\text{C}\text{?}{}^2\text{A}{}_1\text{-}\text{X}\text{?}{}^2\text{A}{}_1$ system of CaNH₂ are reported. Due to the spectral density, individual lines could only be resolved and measured using a filtered fluorescence excitation technique, with a monochromator acting as an optical bandpass filter; 140 line positions were measured in this way and assigned to the parallel K_?1 = 1 subband of what is believed to be the vibrational 0-0 band. The molecular constants were determined from a weighted nonlinear least-squares fit of the line positions.

     

3.

Doppler-limited dye laser excitation spectroscopy of the 401 band of the Ã1A2-X̃1A1 system of D2CS     

《Journal of Molecular Spectroscopy》1987,126(1):29-31

     

4.

Rotational structure of the origin band in the 1A′ ←X1σ+ electronic transition of C4H− and C4D−     

M. PACHKOV  T. PINO  M. TULEJ  F. GUETHE  K. TIKHOMIROV  J. P. MAIER 《Molecular physics》2013,111(4-5):583-588

The rotational structure of the origin band for the ¹A′←X¹σt⁺ electronic transition, lying just below the electron affinity of C⁴H, was recorded by means of a two-colour resonant photodetachment technique. This allowed a determination of the rotational constants in the X¹σt⁺ ground and ¹A′ dipole bound excited state. The low lying A²II excited state of C⁴H is inferred to be the parent of the dipole bound state. The excited electronic state is deduced to have a nonlinear planar structure whereas the ground is linear according to the spectral analysis. The rotational constants have been obtained: B′; = 0.1552(2)cm^?1 for the X¹σt⁺ state, and A′ = 30.73(1), B′ = 0.1587(2), C′ = 0.1581(2)cm^?1 for the ¹A′ state.     

5.

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

《Journal of Molecular Spectroscopy》1986,117(2):331-341

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.     

6.

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

《Journal of Molecular Spectroscopy》1986,117(2):317-330

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.     

7.

The magnetic circular dichroism spectrum of the 1 B 2u ←1 A 1g transition of benzene in the vapour phase     

I.N. Douglas  R. Grinter  A.J. Thomson 《Molecular physics》2013,111(5):1257-1266

The magnetic circular dichroism (MCD) spectrum of the ¹ B _2u ←¹ A _1g transition of benzene has been measured in the vapour phase. Many of the bands due to transitions between single vibronic levels display A terms. It has been shown that the angular momentum arises by vibronic mixing both of the ¹ E _1u state with the ¹ B _1u state and of the ¹ E _2g states with the ¹ A _1g ground state by e _2g vibrations. The magnitudes and signs of the experimental and calculated ratios, A/D, for the A ₀ ⁰ vibronic origin are in excellent agreement. Two strong MCD progressions of opposite sign with B-term dispersion have been observed in regions of low absorption. These are identified with vibronic origins due to the v ₈ and v ₉ e _2g modes. By contrast the MCD spectrum of hexadeuterobenzene vapour has a much lower magneto-rotational strength and displays none of the striking features of the benzene MCD spectrum.     

8.

High-resolution spectrum of the ν9 band and reinvestigation of the ν8 band of cis-CH3ONO     

V. Sironneau  P. Chelin  F. Kwabia Tchana  I. Kleiner  J. Orphal 《Journal of Quantitative Spectroscopy & Radiative Transfer》2012,113(11):1250-1260

The infrared spectrum of methyl nitrite CH₃ONO has been recorded at a spectral resolution of 0.003 cm^?1 using a Fourier-transform spectrometer Bruker IFS125HR. The ν₈ band of the cis isomer has been reinvestigated in the 780–880 cm^?1 spectral range to complete the study made by Goss et al. (2004) [3] and to fit the internal rotor splittings. The BELGI-IR program, which enables us to treat an isolated infrared band for asymmetric molecules containing one internal methyl rotor has been used for the analysis and predictions of spectra. Finally 1036 lines (913 A-type and 123 E-type lines for J≤50 and K_a≤28) have been assigned for the cis isomer and fitted with a standard deviation of 0.00047 cm^?1.Furthermore, for the first time, the ν₉ band of cis-CH₃ONO was investigated in the 540–660 cm^?1 spectral range and rather large internal rotation splittings were also observed at higher J values. For the ν₉ band, the effective approach performed with the BELGI-IR program allowed us to analyze and reproduce 682 lines up to J=50 and K_a=18 with a standard deviation of 0.00051 cm^?1. The multiple vibration–rotation–torsion interactions, which are likely to occur between the excited v₉=1 and v₈=1 states and the torsional manifolds are discussed.     

9.

The optical double resonance spectrum of the B̃1A1 state of Cl2CS     

《Journal of Molecular Spectroscopy》1986,115(1):74-81

     

10.

The Ã-X̃ band system of acetylene: Bands of the short-wavelength region     

《Journal of Molecular Spectroscopy》1986,119(1):137-143

     

11.

The B̃2Σ−g (Πu) ← X̃2A1 system of nitrogen dioxide in neon matrices     

H.D. Bist  J.C.D. Brand  A.R. Hoy  V.T. Jones  R.J. Pirkle 《Journal of Molecular Spectroscopy》1977,66(3):411-420

The $\text{B}\text{?}\text{←}\text{X}\text{?}$ band system of NO₂, ${}^2\text{Σ}{}^{\mathrm{?}}{}_{\mathrm{g}}\text{(π}{}_{\mathrm{u}}\text{) ←}{}^2\text{A}{}_1$, has been measured in absorption in a neon matrix at 6 K, using ¹⁵NO₂ and N¹⁸O₂ in addition to the normal isotope. The spectrum consists essentially of a single, long progression of bands terminating on successive levels of the bending mode in the upper state. Transitions to odd- and even-v₂′ states occur with a uniform intensity distribution indicating that the rotation of the bent ground state of NO₂ about its near-prolate axis is hindered in the matrix. The observations strongly suggest that the top axis of the molecule coincides with a C₂ axis of neon crystals in the polycrystalline matrix. Relative to the vapor absorption the matrix spectrum is red shifted by about 150 cm^?1, the crystal field parameter V₂ and principal constants of the $\text{B}\text{?}$ state of ¹⁴N¹⁶O₂ in neon being

$\text{T}{}_{010}\text{14 571 cm}{}^{\mathrm{?1}}\text{: x}{}_{22}\text{, ?0.3 cm}{}^{\mathrm{?1}}\text{;}$

$\text{w}{}_2\text{460.2 cm}{}^{\mathrm{?1}}\text{: V}{}_2\text{, 80 cm}{}^{\mathrm{?1}}\text{.}$

     

12.

High-resolution spectroscopy on the c1Π ← a1Δ transition in NH     

《Journal of Molecular Spectroscopy》1986,115(1):88-104

The spectrum of the c¹Π, v = 0 ← a¹Δ, v = 0 band of the NH molecule at λ = 324 nm has been investigated under high resolution by laser-induced fluorescence in a molecular beam. From an analysis of the spectra we obtained: the magnetic dipole interaction constants a_N,H and the electric quadrupole constants eQq_1,2 for both electronic states, the improved values for the Λ-doubling constants q_π, q_π^D, and q_π^H for the c¹Π state, and rotational constants for both electronic states up to a third-order centrifugal distortion. Also, the Λ-doubling in the a¹Δ state could be determined.     

13.

Infrared spectrum of the Ar-CO complex: observation of the v co = 2 ← 0 band at 4260 cm −1     

A. R. W. McKELLAR 《Molecular physics》2013,111(2):111-115

The spectrum of the weakly-bound van der Waals complex Ar-CO has been observed for the first time in the region of the CO vibrational overtone, using a long-path (180 m) low-temperature (64 K) absorption cell and a Fourier transform infrared spectrometer. The appearance of the spectrum was very similar to that studied previously in the v _co = 1 ← 0 region. However, it was very much weaker, so a detailed analysis was only possible for the relatively uncongested K = 1 ← 0 and 0 ← 1 subbands. The parameters determined here for these sub-bands should help to constrain the C-O bond length dependence of the Ar-CO intermolecular potential in future theoretical models.     

14.

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

《Journal of Molecular Spectroscopy》1987,124(1):130-138

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.     

15.

The 1B2 ← 1A1 transition of aniline in low-temperature matrices     

《Journal of Molecular Spectroscopy》1971,39(2):352-356

     

16.

High-resolution inverse Raman spectroscopy of the ν1 band of water vapor     

《Journal of Molecular Spectroscopy》1986,119(1):11-21

The Raman spectrum of the ν₁ band of water vapor at 7 Torr and 296 K, and at 84 Torr and 404 K, has been measured using high-resolution inverse Raman spectroscopy. The frequencies and relative intensities of the observed transitions are compared to a spectral model based on infrared data. Self-broadening coefficients have been determined for 22 lines from J = 0 to J = 8.     

17.

Diode laser spectroscopy of the BO2 radical: The κ2Σ ← 2Π32 transition of the ν2 fundamental band     

《Journal of Molecular Spectroscopy》1986,116(2):450-457

     

18.

A theoretical study of the 21Ag ← 11Ag two-photon transition and its vibronic band in trans-stilbene     

JONNA STÅLRING  LAURA GAGLIARDI  PER-ÅKE MALMQVIST  ROLAND LINDH 《Molecular physics》2013,111(11):1791-1796

The two-photon spectrum of the 2¹A_g ← 1¹A_g transition in trans-stilbene has been calculated at the complete active space self-consistent field (CASSCF) level of theory. Energies were obtained at the complete active space second-order perturbation (CASPT2) level of theory, while the geometries of both the initial and final states were optimized at the CASSCF level. The energy and the geometry optimizations were performed using an active space of 14 electrons in 14 active π orbitals. The vibrational frequencies of both states and the two-photon transition (TPT) cross-section were calculated with a smaller active space where the two lowest π orbitals were kept inactive. A newly implemented algorithm, in the quantum chemical package Molcas was used to determine the two-photon transition intensity. This method requires only the linear response of the CASSCF wavefunction. Furthermore, the vibronic structure of this TPT was studied. The Franck-Condon factors were obtained by calculating the overlap between the vibrational states involved, which were determined from the force fields of both the initial and final states, at the CASSCF level of theory. The results are in agreement with experiment.     

19.

High-resolution infrared spectrum of hydrogen peroxide: The ν6 fundamental band     

《Journal of Molecular Spectroscopy》1986,117(1):46-59

The infrared spectrum of the ν₆ asymmetric deformation band of hydrogen peroxide (H₂O₂) was studied in the region 1100–1350 cm⁻¹ using the two techniques of Fourier transform spectroscopy at 0.02 cm⁻¹ resolution and tunable diode laser spectroscopy at Doppler-limited resolution. Details of the wavelength calibration procedures adopted are discussed. For the first time, accurate values of the molecular parameters of this torsionally doubled, vibrational band were obtained. A total of 708 assigned transitions have been analyzed to yield a set of 14 rovibrational constants for the lower torsion-vibration level (SD = 0.00487 cm⁻¹) and 13 rovibrational constants for the upper torsion-vibration level (SD = 0.00382 cm⁻¹). These hybrid bands are primarily A type with band centers at 1264.5812 ± 0.0009 and 1273.6830 ± 0.0009 cm⁻¹. Because of the absence of observed perturbations, the derived molecular constants can be used to calculate transition frequencies with a high degree of accuracy up to K_a = 6.     

20.

The high-resolution spectrum of the ν1 + ν2 band of NO2: A spin-induced perturbation in the ground state     

《Journal of Molecular Spectroscopy》1987,125(1):99-114

The spectrum of the ν₁ + ν₂ band of NO₂ has been studied with a resolution of 0.025 cm⁻¹. Spin-rotation constants and rotational constants are reported. An interesting perturbation has been found in the ground state of the molecule which occurs when the K_a = 0 and K_a = 2 levels become accidentally nearly degenerate around N = 42. An explanation of this interaction is presented.     

		Main parameters
	$\text{X}\text{?}{}^2\text{A}{}_1$	$\text{C}\text{?}{}^2\text{A}{}_1$
$\text{T}{}_{\mathrm{k?1}}\text{= 1}$	3-	17375.129(5)
B	0.30079(6)	0.30562(6)
C	0.29319(6)	0.29789(8)
$\text{?}{}_{\mathrm{aa}}$	3-	?0.66(4)
$\text{?}{}_{\mathrm{bb}}$	3-	?0.0356(8)
$\text{?}{}_{\mathrm{cc}}$	3-	?0.0453(8)

Rotational structure of the origin band in the 1A′ ←X1σ+ electronic transition of C4H− and C4D−

The rotational structure of the origin band for the ¹A′←X¹σt⁺ electronic transition, lying just below the electron affinity of C⁴H, was recorded by means of a two-colour resonant photodetachment technique. This allowed a determination of the rotational constants in the X¹σt⁺ ground and ¹A′ dipole bound excited state. The low lying A²II excited state of C⁴H is inferred to be the parent of the dipole bound state. The excited electronic state is deduced to have a nonlinear planar structure whereas the ground is linear according to the spectral analysis. The rotational constants have been obtained: B′; = 0.1552(2)cm^?1 for the X¹σt⁺ state, and A′ = 30.73(1), B′ = 0.1587(2), C′ = 0.1581(2)cm^?1 for the ¹A′ state.     

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 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 magnetic circular dichroism spectrum of the 1 B 2u ←1 A 1g transition of benzene in the vapour phase

The magnetic circular dichroism (MCD) spectrum of the ¹ B _2u ←¹ A _1g transition of benzene has been measured in the vapour phase. Many of the bands due to transitions between single vibronic levels display A terms. It has been shown that the angular momentum arises by vibronic mixing both of the ¹ E _1u state with the ¹ B _1u state and of the ¹ E _2g states with the ¹ A _1g ground state by e _2g vibrations. The magnitudes and signs of the experimental and calculated ratios, A/D, for the A ₀ ⁰ vibronic origin are in excellent agreement. Two strong MCD progressions of opposite sign with B-term dispersion have been observed in regions of low absorption. These are identified with vibronic origins due to the v ₈ and v ₉ e _2g modes. By contrast the MCD spectrum of hexadeuterobenzene vapour has a much lower magneto-rotational strength and displays none of the striking features of the benzene MCD spectrum.     

High-resolution spectrum of the ν9 band and reinvestigation of the ν8 band of cis-CH3ONO

The infrared spectrum of methyl nitrite CH₃ONO has been recorded at a spectral resolution of 0.003 cm^?1 using a Fourier-transform spectrometer Bruker IFS125HR. The ν₈ band of the cis isomer has been reinvestigated in the 780–880 cm^?1 spectral range to complete the study made by Goss et al. (2004) [3] and to fit the internal rotor splittings. The BELGI-IR program, which enables us to treat an isolated infrared band for asymmetric molecules containing one internal methyl rotor has been used for the analysis and predictions of spectra. Finally 1036 lines (913 A-type and 123 E-type lines for J≤50 and K_a≤28) have been assigned for the cis isomer and fitted with a standard deviation of 0.00047 cm^?1.Furthermore, for the first time, the ν₉ band of cis-CH₃ONO was investigated in the 540–660 cm^?1 spectral range and rather large internal rotation splittings were also observed at higher J values. For the ν₉ band, the effective approach performed with the BELGI-IR program allowed us to analyze and reproduce 682 lines up to J=50 and K_a=18 with a standard deviation of 0.00051 cm^?1. The multiple vibration–rotation–torsion interactions, which are likely to occur between the excited v₉=1 and v₈=1 states and the torsional manifolds are discussed.     

The B̃2Σ−g (Πu) ← X̃2A1 system of nitrogen dioxide in neon matrices

The $\text{B}\text{?}\text{←}\text{X}\text{?}$ band system of NO₂, ${}^2\text{Σ}{}^{\mathrm{?}}{}_{\mathrm{g}}\text{(π}{}_{\mathrm{u}}\text{) ←}{}^2\text{A}{}_1$, has been measured in absorption in a neon matrix at 6 K, using ¹⁵NO₂ and N¹⁸O₂ in addition to the normal isotope. The spectrum consists essentially of a single, long progression of bands terminating on successive levels of the bending mode in the upper state. Transitions to odd- and even-v₂′ states occur with a uniform intensity distribution indicating that the rotation of the bent ground state of NO₂ about its near-prolate axis is hindered in the matrix. The observations strongly suggest that the top axis of the molecule coincides with a C₂ axis of neon crystals in the polycrystalline matrix. Relative to the vapor absorption the matrix spectrum is red shifted by about 150 cm^?1, the crystal field parameter V₂ and principal constants of the $\text{B}\text{?}$ state of ¹⁴N¹⁶O₂ in neon being

$\text{T}{}_{010}\text{14 571 cm}{}^{\mathrm{?1}}\text{: x}{}_{22}\text{, ?0.3 cm}{}^{\mathrm{?1}}\text{;}$

$\text{w}{}_2\text{460.2 cm}{}^{\mathrm{?1}}\text{: V}{}_2\text{, 80 cm}{}^{\mathrm{?1}}\text{.}$

     

High-resolution spectroscopy on the c1Π ← a1Δ transition in NH

The spectrum of the c¹Π, v = 0 ← a¹Δ, v = 0 band of the NH molecule at λ = 324 nm has been investigated under high resolution by laser-induced fluorescence in a molecular beam. From an analysis of the spectra we obtained: the magnetic dipole interaction constants a_N,H and the electric quadrupole constants eQq_1,2 for both electronic states, the improved values for the Λ-doubling constants q_π, q_π^D, and q_π^H for the c¹Π state, and rotational constants for both electronic states up to a third-order centrifugal distortion. Also, the Λ-doubling in the a¹Δ state could be determined.     

Infrared spectrum of the Ar-CO complex: observation of the v co = 2 ← 0 band at 4260 cm −1

The spectrum of the weakly-bound van der Waals complex Ar-CO has been observed for the first time in the region of the CO vibrational overtone, using a long-path (180 m) low-temperature (64 K) absorption cell and a Fourier transform infrared spectrometer. The appearance of the spectrum was very similar to that studied previously in the v _co = 1 ← 0 region. However, it was very much weaker, so a detailed analysis was only possible for the relatively uncongested K = 1 ← 0 and 0 ← 1 subbands. The parameters determined here for these sub-bands should help to constrain the C-O bond length dependence of the Ar-CO intermolecular potential in future theoretical models.     

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.     

High-resolution inverse Raman spectroscopy of the ν1 band of water vapor

The Raman spectrum of the ν₁ band of water vapor at 7 Torr and 296 K, and at 84 Torr and 404 K, has been measured using high-resolution inverse Raman spectroscopy. The frequencies and relative intensities of the observed transitions are compared to a spectral model based on infrared data. Self-broadening coefficients have been determined for 22 lines from J = 0 to J = 8.     

A theoretical study of the 21Ag ← 11Ag two-photon transition and its vibronic band in trans-stilbene

The two-photon spectrum of the 2¹A_g ← 1¹A_g transition in trans-stilbene has been calculated at the complete active space self-consistent field (CASSCF) level of theory. Energies were obtained at the complete active space second-order perturbation (CASPT2) level of theory, while the geometries of both the initial and final states were optimized at the CASSCF level. The energy and the geometry optimizations were performed using an active space of 14 electrons in 14 active π orbitals. The vibrational frequencies of both states and the two-photon transition (TPT) cross-section were calculated with a smaller active space where the two lowest π orbitals were kept inactive. A newly implemented algorithm, in the quantum chemical package Molcas was used to determine the two-photon transition intensity. This method requires only the linear response of the CASSCF wavefunction. Furthermore, the vibronic structure of this TPT was studied. The Franck-Condon factors were obtained by calculating the overlap between the vibrational states involved, which were determined from the force fields of both the initial and final states, at the CASSCF level of theory. The results are in agreement with experiment.     

High-resolution infrared spectrum of hydrogen peroxide: The ν6 fundamental band

The infrared spectrum of the ν₆ asymmetric deformation band of hydrogen peroxide (H₂O₂) was studied in the region 1100–1350 cm⁻¹ using the two techniques of Fourier transform spectroscopy at 0.02 cm⁻¹ resolution and tunable diode laser spectroscopy at Doppler-limited resolution. Details of the wavelength calibration procedures adopted are discussed. For the first time, accurate values of the molecular parameters of this torsionally doubled, vibrational band were obtained. A total of 708 assigned transitions have been analyzed to yield a set of 14 rovibrational constants for the lower torsion-vibration level (SD = 0.00487 cm⁻¹) and 13 rovibrational constants for the upper torsion-vibration level (SD = 0.00382 cm⁻¹). These hybrid bands are primarily A type with band centers at 1264.5812 ± 0.0009 and 1273.6830 ± 0.0009 cm⁻¹. Because of the absence of observed perturbations, the derived molecular constants can be used to calculate transition frequencies with a high degree of accuracy up to K_a = 6.     

The high-resolution spectrum of the ν1 + ν2 band of NO2: A spin-induced perturbation in the ground state

The spectrum of the ν₁ + ν₂ band of NO₂ has been studied with a resolution of 0.025 cm⁻¹. Spin-rotation constants and rotational constants are reported. An interesting perturbation has been found in the ground state of the molecule which occurs when the K_a = 0 and K_a = 2 levels become accidentally nearly degenerate around N = 42. An explanation of this interaction is presented.