The microwave spectrum of the SF radical

The rotational spectrum of the SF radical in the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state was observed by using a source-modulation microwave spectrometer with a 1-m-long discharge cell. The SF radical was generated directly in the cell by a dc discharge in an $\text{OCS}\text{CF}{}_4$ mixture. A previous measurement of the microwave spectrum in the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ state was also extended to higher-J transitions. The least-squares analysis of all the observed spectral lines gave the B₀ rotational constant and the D₀ centrifugal distortion constant to be 16 576.9140(46) and 0.02924(10) MHz, respectively, where the values in parentheses denote 2.5 times the standard deviations. The Λ-doubling constant p_v was found to be extremely small, 3.409(44) MHz, and it was presumed that contributions of ²Σ⁺ and ²Σ^? states to the Λ doubling cancel each other. All the four fluorine hyperfine coupling constants were also determined, from which the spin density on the F atom was calculated to be 0.13.     

Spectrum and structure of the He2 molecule: Characterization of the singlet and triplet states associated with the UAO's 4s, 4dσ, 4dπ, and 4dδ

The emission spectrum of the He₂ molecule has been rephotographed in the ～4000–～5700 Å region and the $\text{4d(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}\text{) → 2pπ}{}^3\text{Π}{}_{\mathrm{g}}$, $\text{4d(}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^1\text{Π}{}_{\mathrm{u}}\text{,}{}^1\text{Δ}{}_{\mathrm{u}}\text{) → 2pπ}{}^1\text{Π}{}_{\mathrm{g}}$, $\text{4s}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 2pπ}{}^3\text{Π}{}_{\mathrm{g}}$ and $\text{4s}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 2pπ}{}^1\text{Π}{}_{\mathrm{g}}$ transitions analyzed. The 4dδj³Δ_u, 4dπj³Π_u, $\text{4dσj}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ and $\text{4sh}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ states have been characterized through v = 2 and the 4dδJ¹Δ_u, 4dπJ¹Π_u, $\text{4dσJ}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$, and $\text{4sH}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ states for v = 0. The term levels for these perturbed and l-uncoupled states have been confirmed (a) by analyses of bands with common levels from Δv = 0, ±1 sequences and (b) by analyses of the transitions between the above states from 4d and 4s and the $\text{c}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ and $\text{C}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ states associated with 3pσ. Molecular constants are reported which have been partially corrected for the effects of l-uncoupling and the homogeneous perturbations between the state pairs J, H and j, h.     

Microwave spectroscopy of the CCl radical

The CCl radical was generated by a dc glow discharge in CCl₄, and rotational transitions of C³⁵Cl in both ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ were observed in the mm-wave region by using a source modulation microwave spectrometer. From an analysis of the observed spectra the magnetic and electric quadrupole hyperfine coupling constants of the ³⁵Cl nucleus were determined precisely. The Λ-doubling constant p₀ was determined to be positive, indicating that unknown ²Σ^? excited electronic states are making dominant contributions to the Λ doubling in the ground state. The previous diode-laser result [J. Mol. Spectrosc.85, 416–426 (1981)] was reanalyzed by using improved wavelength standards and by fixing the ground-state parameters to the present microwave values including the B₀ rotational constant 20 797.1725(38) MHz. The vibration-rotation constant α^B and the equilibrium bond length r_e were thus determined to be 0.006 768 2(48) cm^?1 and 1.645 218(16) Å, respectively, with 2.5 times standard deviations in parentheses. The spin density on the chlorine atom was estimated to be about 0.20 from the observed hyperfine coupling constants.     

Excited vibrational state microwave spectra,structure, and force-field of trifluorosilane

The J = 2?1 microwave spectrum of six isotopic species of HSiF₃ has been observed and assigned in excited states of five of the six fundamental vibrations. The assignment is based on relative intensities, double resonance experiments, and trial anharmonic force constant calculations. Analysis of the spectra leads to experimental values for five of the $\text{α}{}_{\mathrm{r}}{}^{\mathrm{B}}$ constants, all three l-doubling constants q_t, one Fermi resonance constant φ₂₃₃, and one zeta constant $\text{ζ}{}_{\mathrm{6,\; 6}}{}^{\mathrm{(z)}}$.The harmonic force field has been refined to all the available data on vibration wavenumbers, centrifugal distortion constants, and zeta constants. The cubic anharmonic force field has been refined to the data on $\text{α}{}_{\mathrm{r}}{}^{\mathrm{B}}$ and q_t constants, using two models: a valence force model with two cubic force constants for SiH and SiF stretching, and a more sophisticated model. With the help of these calculations, the following equilibrium structure has been determined: $\text{r}{}_{\mathrm{e}}\text{(}\text{SiH}\text{) = 1.4468(±5)}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(}\text{SiF}\text{) = 1.5624(±1)}\text{A}\text{?}$, ∠HSiF = 110.64(±3)°,     

Diode laser spectroscopy of the CCl radical

Vibration-rotation transitions of the fundamental band have been observed for both C³⁵Cl and C³⁷Cl in the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ states by using an infrared diode laser spectrometer with Zeeman modulation. A few lines of the “hot” band (v = 2 ← 1) have also been recorded for C³⁵Cl. From an analysis of the observed spectra improved values were obtained for the vibrational harmonic frequency and anharmonicity constant, rotational constants, and Λ-doubling parameters. It was found necessary to take into account centrifugal distortion effects on the spin-orbit coupling constant A in the analysis, which gave $\text{(}\text{dA}\text{dr}\text{)}{}_{\mathrm{<mtext>e</mtext>}}\text{r}{}_{\mathrm{<mtext>e</mtext>}}$ to be ?176 ± 38 or ?125 ± 38 cm^?1, depending upon whether ²Σ^? or ²Σ⁺ states contribute more to the Λ-type doubling. The equilibrium internuclear distance r_e was calculated from the derived rotational constants to be 1.64506 ± 0.00016 Å.     

The microwave spectrum of the SiCl radical

The microwave spectrum of ²⁸Si³⁵Cl, the most abundant isotopic species of the silicon monochloride radical, was observed in both the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ spin states of the ground vibronic state. The SiCl radical was produced in a flow cell by a dc discharge in SiCl₄. The observed transitions were $\text{J =}\text{7}\text{2}\text{←}\text{5}\text{2}\text{up to}\text{21}\text{2}\text{←}\text{19}\text{2}$ for both the spin states, and the observed frequencies were subjected to the least-squares analysis to yield accurate molecular constants as follows: B₀ = 7652.3048(23), D₀ = 0.007017(14), A_J = ?0.8392(16), p₀ + 2q₀ = 138.660(98), q₀ = 0.20(17), $\text{a + (b + c)}\text{2}\text{= 37.50(28)}$, $\text{a ? (b + c)}\text{2}\text{= 49.84(73)}$, b = 9(12), d = 46.40(94), and eQq₁ = ?23.13(96), all in MHz with 3σ in parentheses. The positive sign of the Λ-doubling constant, p₀, indicates that the contributions of ²Σ^? states dominate over those of ²Σ⁺ states. The spin and orbital averages of the unpaired-electron distribution were calculated from the observed hyperfine coupling constants and were discussed in terms of the electronic structure of the molecule.     

Microwave spectrum of the IO radical

The two lowest rotational transitions of the IO radical in the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ ground electronic state have been observed by means of a Stark modulated spectrometer. The effective rotational constants in the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ state, the centrifugal distortion constant, the axial component of the magnetic hyperfine interaction, and the nuclear electric quadrupole coupling constant are determined accurately. It was necessary to take into account the second-order effects from the matrix elements off-diagonal in J for the analysis of the hyperfine structure. An equilibrium internuclear distance r_e is calculated to be 1.8677 ± 0.0028 Å from the effective rotational constant $\text{B}{}_0\text{(}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{)}$, combined with α₃ from the A²Π → X²Π transition.     

The A-X system of Br2+ radical cations

The ²Π_u-X²Π_g transition in Br₂⁺ was reexamined using dispersed laser-induced fluorescence, and emission spectroscopy in a seeded molecular beam. New constants are derived, confirming the large difference between $\text{A}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{A}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, and reconciling the emission spectrum with photoelectron data.     

3Σu−-3Σu+ coupling in the O2B3Σu− predissociation

The role of $\text{B}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{-2}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ spin-orbit mixing in the O₂ Schumann-Runge predissociation is investigated. The $\text{2}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state is found to cross the $\text{B}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}$ state near 2.0 Å with an interaction matrix element of approximately 55 cm^?1. This state contributes to the widths of the Bv ≥ 6 levels, but introduces only small level shift perturbations. When the partial widths due to the ${}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{-}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ interaction are added to the previously calculated widths due to the ⁵Π_u, ³Π_u, and ¹Π_u states, reasonable agreement is obtained with experimental measurements on O¹⁶O¹⁶ and O¹⁸O¹⁸. The possibility of non-Lorentzian line profiles and the dependence of the width on rotational quantum number is investigated. The approximation of the spin-orbit matrix element by its value at the crossing point is shown to be a good approximation for calculating the second difference perturbations.     

Energy levels of low lying triplet states of N2 from infrared emission studies

A theoretical model used to describe the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}$ and B³Π_g states of N₂ is presented. Using recently acquired high resolution spectra of the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{→ B}{}^3\text{Π}{}_{\mathrm{g}}$ (0-0) band, rotational energy levels of the v = 0 vibrational levels of these two states are generated with this model. These levels are in excellent agreement with those obtained using a combination differences technique. The precision of the model generated levels is 0.01 cm^?1. The previously unpublished rotational levels of Dieke and Heath for the $\text{A}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$, B³Π_g and C³Π_u states are referenced to the $\text{N}{}_2\text{X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ (v = 0, J = 0) ground level and tabulated here. Estimates of the precision of their work are made.     

Infrared diode laser spectroscopy of the NS radical

The v = 1 ← 0 vibration-rotation bands of the NS radical in the $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ electronic states were observed by using a tunable diode laser. From the least-squares analysis the band origins were determined to be 1204.2755(12) and 1204.0892(19) cm^?1, respectively, for $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$. The rotational and centrifugal distortion constants and the internuclear distance in the X²Π electronic state were obtained as follows: B_e = 0.775549(10) cm^?1, D_e = 0.00000129(33) cm^?1, and $\text{r}{}_{\mathrm{e}}\text{= 1.49403(4)}\text{A}\text{?}$, with three standard deviations indicated in parentheses.     

The infrared part of the C2 Phillips system (2.3–0.9 μm)

Line positions and molecular constants for the 0-0, 1-0, 2-0, 0-1, 2-1, 3-1, 0-2, 1-2, and 4-2 bands of the C₂ Phillips system ($\text{A}{}^1\text{Π}{}_{\mathrm{u}}\text{-X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$) are reported. Among them, five bands have not been reported previously. Rotational perturbations have been observed in the previously unobserved v = 1 level of the $\text{A}{}^1\text{Π}{}_{\mathrm{u}}$ state. This state is perturbed by the $\text{c}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state which was discovered by Ballik and Ramsay. These observations provide new information regarding the perturbing state. In particular, the minimum of the potential energy for the $\text{c}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state has been found to be at 9227.4 cm^?1 instead of 13 310 cm^?1, which was the previous T_e value for this electronic state.     

Infrared diode laser spectroscopy of the CF radical

The fundamental bands of the CF radical in the $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ electronic states were observed by using an infrared tunable diode laser as a source. Zeeman modulation could be used in detecting lines not only in the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ state, but also in ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, because the CF radical deviates considerably from Hund's case (a). From the least-squares analysis of the observed spectra, the following molecular constants were obtained: B_e = 1.416 704 (37) cm^?1, α_e = 0.018 419 (50) cm^?1, $\text{r}{}_{\mathrm{e}}\text{= 1.271 977 (17)}\text{A}\text{?}$, D_e = 6.68 (15) × 10^?6cm^?1, p₀ = 0.008 580 (21) cm^?1, p₁ = 0.008 52 (11) cm^?1, and $\text{ν}{}_0\text{= 1286.1281 (5)}\text{cm}{}^{\mathrm{?1}}$, with three standard errors in parentheses.     

The spectrum of HeNe+

Discharges through mixtures of helium and neon show two band groups near 4250 and 4100 Å as first observed by Druyvesteyn. These bands, assigned to the HeNe⁺ ion by Tanaka, Yoshino, and Freeman, have been studied under high resolution and have been fairly completely analyzed. The upper state of the transition is a very weakly bound state resulting from $\text{He}{}^{\mathrm{+}}\text{(}{}^2\text{S) +}\text{Ne}\text{(}{}^1\text{S}{}_0\text{)}$. There are two lower states resulting from the two components of $\text{Ne}{}^{\mathrm{+}}\text{(}{}^2\text{P) +}\text{He}\text{(}{}^1\text{S}{}_0\text{)}$. The upper of these two (${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) is also very weakly bound while the lower of the two, the ²Σ⁺ ground state, has a dissociation energy of 0.69 eV and an r_e value of 1.30 Å. All bands in both band groups show four branches designated R_ff, Q_ef, Q_fe, and P_ee. From their analysis the rotational constants in the various vibrational levels of the three electronic states have been determined. While no spin splitting in the B²Σ⁺ state has been found the ground state X²Σ shows a very large spin splitting and the $\text{A}{}_2{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state a very large $\text{Ω-type}$ doubling. The vibrational numberings in all these states were established by the study of the spectrum of ³HeNe⁺. At the same time the hyperfine structure observed in all lines of ³HeNe⁺ confirmed the nature of the upper state B²Σ⁺ as resulting from He⁺ + Ne, i.e., by charge exchange from the ground state. The ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ component of the ²Π state has not been observed, presumably because of low intensity.     

The spectrum of HeAr+

Two band groups near 1450 Å, first observed by Tanaka, Yoshino, and Freeman (J. Chem. Phys.62, 4484–4496 (1975)) in discharges through mixtures of helium and argon and assigned by them to the HeAr⁺ ion, were studied under high resolution. Like the similar spectrum of HeNe⁺ previously investigated, the spectrum of HeAr⁺ is a charge transfer spectrum. The upper state B²Σ⁺ of both band groups is derived from $\text{He}{}^{\mathrm{+}}\text{(}{}^2\text{S) +}\text{Ar}\text{(}{}^1\text{S)}$ while the two lower states $\text{A}{}_2{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and X²Σ⁺ are derived from $\text{He}\text{(}{}^1\text{S) +}\text{Ar}{}^{\mathrm{+}}\text{(}{}^2\text{P)}$. All three states are very weakly bound, the two lower states even more weakly than the upper state. Unlike HeNe⁺ most of the HeAr⁺ bands are violet shaded. In the longward band group each band shows only three branches while in the shortward group there are four. The former observation shows that the $\text{A}{}_2{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ state behaves like a ²Σ^? state with γ_v ≈ 0. The B, D, γ, p, and ΔG values of all states were evaluated. While the B_v values of upper and lower states are nearly equal, the D_v values are quite different and this difference accounts for the violet shading of most of the bands even when B′_v is slightly smaller than B″_v; it also accounts for some of the extraheads and linelike features in the rotational structure. As in HeNe⁺ the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ component of ²Π was not observed.     

The emission spectra of H35Cl+, H37Cl+, D35Cl+, and D37Cl+ in the region 2700–4100 Å

The $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}\text{-X}{}^2\text{Π}$ emission spectrum of HCl⁺ has been measured and analyzed for four isotopic combinations. These analyses extend previous work and provide rotational constants for the v = 0–2 levels of the ground state and for the v = 0–9 levels of the excited state. RKR potentials have been determined for both states, although the upper state could not be fitted precisely to such a model. Calculated relative intensities based on these potentials demonstrated that the electronic transition moment must change rapidly with lower state vibrational quantum number. Although considerable caution should be exercised in applying the concept of equilibrium constants to the $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}$ state, the following are the best estimates of these constants (in cm^?1) for the $\text{X}{}^2\text{Π}$ state of H³⁵Cl⁺: B_e = 9.9406, ω_e = 2673.7, A_e = ? 643.7, and $\text{r}{}_{\mathrm{e}}\text{= 1.315}\text{A}\text{?}$. For the $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}$ state of H³⁵Cl: T_e = 28 628.08, B_e ～ 7.505, ω_e ～ 1606.5, and $\text{r}{}_{\mathrm{e}}\text{= 1.514}\text{A}\text{?}$.     

Photoluminescence of the A2Π-X2Σ+ system of the yttrium oxide molecule

A cw dye laser, tunable in the region 570–620 nm, has been used to excite photoluminescence in the A²Π-X²Σ⁺ system of the YO molecule. Two methods have been used to obtain spectra. They are (i) photoluminescence and (ii) spectrally selective excitation spectroscopy. The latter maintains the simplicity of photoluminescence, but has higher resolution. The spectra obtained at medium resolution (～0.05 nm) have been surveyed and the identification of transitions has been outlined. A method was devised in which known lower state constants were used in calculating approximate upper state constants whenever the laser simultaneously excited coincident rotational transitions in the same band. From these calculations, an approximate value of α′_e was calculated which was found to be close to, but slightly larger than values previously computed from the Pekeris formula. Many examples of collisional transfer were observed. In particular, maximum transfer from ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ to ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ was always observed to involve an increase of one unit in the vibrational quantum number. No transfer was observed between opposite parity components of Λ doublets, in spite of their closeness in energy, indicating that the symmetry of the electronic eigenfunctions was unaffected by collisions. Reanalysis of previous high resolution data has shown that, when the contribution of Λ-doubling parameters to the separation of the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ states is taken into account, the value of the spin-orbit coupling constant, A, changes significantly. It was also found necessary to include the constant, A_D, to account for the effect of centrifugal distortion on the spin-orbit interaction.     

Predissociation and Λ-doubling in the even-parity Rydberg states of the nitrogen molecule

Predissociations in the y¹Π_g and $\text{x}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$ Rydberg states of N₂ (configurations $\text{1π}{}_{\mathrm{u}}{}^{\mathrm{?1}}\text{4pσ}$ and $\text{1π}{}_{\mathrm{u}}{}^{\mathrm{?1}}\text{3pπ}$, respectively) and their likely causes, are discussed. Peaking of rotational intensity at unusually low J values, without sharp breaking off, is interpreted as due to case c^? or case cⁱ predissociation. Λ doubling in the y state, attributed to interactions with the $\text{x}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$ state and with another, ¹Σ⁺, state of the same electron configuration as x, is analyzed. From this analysis the location of the (unobserved) ${}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ state, here labeled x′, is obtained. It is concluded that the predissociation in the Π⁺ levels of the y state is an indirect one mediated by the interaction with x′ coupled with predissociation of x′ by a ${}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$ state dissociating to ${}^4\text{S +}{}^2\text{P}$ atoms: combined, however, with perturbation of the y state by the k¹Π_g Rydberg state (configuration $\text{3σ}{}_{\mathrm{g}}{}^{\mathrm{?1}}\text{4dπ}$), whose Π⁺ levels are completely predissociated.     

Analysis of the B′3Σu− → B3Πg (0,0) emission band of molecular nitrogen

The (0,0) band of the $\text{B′}\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{→ B}{}^3\text{Π}{}_{\mathrm{g}}$ emission (Infrared Afterglow) system of molecular nitrogen has been recorded with a resolution of 0.046 cm^?1 and a line position accuracy of 0.007 cm^?1. Six hundred and seventy-two lines are tabulated into a line list for the 1.53 μm (low-resolution) emission feature. Of these, 482 are assigned as members of the 27 branches of the B′ → B transition, while 150 are identified with the 1PG (3,6) band. Molecular constants for the v = 0 levels of the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}$ and B³Π_g states have been computed and tabulated.     

The rotational spectrum and molecular parameters of ClO in the v=0 and v=1 states

The $\text{J =}\text{9}\text{2}\text{←}\text{7}\text{2}$, ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, ground vibrational state transitions of ³⁵ClO and ³⁷ClO and the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, excited vibrational state transitions of ³⁵ClO have been observed in the 164–167 GHz region. Additional measurements have also been made on the $\text{J =}\text{3}\text{2}\text{←}\text{1}\text{2}$ and $\text{J =}\text{5}\text{2}\text{←}\text{3}\text{2}$ transitions of both the ground and excited vibrational states. All measurements were made using millimeter oscillators which were phase locked to harmonics of a Hewlett-Packard microwave spectrometer's X-band source. Λ-doubling splitting of a few ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ transitions was resolved.When magnetic and nuclear quadrupole hyperfine terms off-diagonal in J and $\text{Ω}$ in the Hund's case (a) representation were included in addition to the usual diagonal terms, an excellent fit to all of our observed transitions resulted. The most significant change from previously determined parameters is the centrifugal distortion constant D for which the values, D₀ = 0.03972(26) MHz for ³⁵ClO, D₀ = 0.03888(32) MHz for ³⁷ClO and D₁ = 0.0395(21) MHz for ³⁵ClO are obtained. Values of 1.56959(1) Å for the equilibrium bond length and 854(7) cm^?1 for the equilibrium vibrational frequency are derived from the measured spectra. In addition, values for the Λ-doubling constant β_p and the quadrupole coupling constant eQq₂ were derived from the measured spectra for the first time.