Energies and orbital sizes for some Rydberg and valence states of the nitrogen molecule

Accurate SCF computations are reported on the Rydberg states of N₂ of electron configurations $\text{---1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$, $\text{---1π}{}_{\mathrm{u}}{}^3\text{3σ}{}_{\mathrm{u}}$, and ---3σ_g2π_g, also on the valence states of the configuration $\text{---1π}{}_{\mathrm{u}}{}^3\text{1π}{}_{\mathrm{g}}$. The Rydberg state calculations supplement those of Lefebvre-Brion and Moser. A comparison is made between the $\text{---1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$ states and the parallel set of states of the $\text{1π}{}_{\mathrm{u}}{}^3\text{1π}{}_{\mathrm{g}}$ configuration. This comparison shows a sharp difference in the ¹Σ⁺ states of the two configurations, the ¹Σ⁺ state being very high in the latter but relatively low in the former configuration. Recknagel coefficients are given for the several states of the two configurations; as expected, these are much smaller for the $\text{1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$ configuration. Also, the ¹Δ state is relatively lower for the latter configuration.     

Lifetime of electronic states of CO2+

The radiative lifetimes of the $\text{A}\text{?}{}^2\text{Π}{}_{\mathrm{u}}$ and $\text{B}\text{?}{}^2\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ states of CO₂⁺ were measured by means of the delayed coincidence method. Excitation was performed by a pulsed electron beam incident on CO₂. The results of these measurements are 115 ± 5 nsec for the $\text{A}\text{?}{}^2\text{Π}{}_{\mathrm{u}}$ state and 126 ± 3 nsec for the $\text{B}\text{?}{}^2\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state.     

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.     

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.     

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.     

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.     

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.     

Model calculation of the electronic structure and spectroscopy of Hg2

Energy curves and transition moments of the excited valence states of Hg₂ were obtained in a model calculation based on calculated Mg₂ energy levels and the assumption that the asymptotic spin-orbit matrix elements for the Hg atom are applicable to the molecular states. The spin-orbit and orbital-rotational interaction of the excited states of Hg₂ is analyzed in both a Hund's case (c) and (a) representation. The intermediate (a) → (c) transition moments are obtained as a function of the internuclear distance. The effect of the orbital-rotational interaction which introduces Hund's case (b) and (e) couplings is found to be small for transitions among excited states under the conditions normally encountered for populating excimer states.Using the energy level positions and transition moments, the observed spectra and predicted spectra are compared for both radiative transitions including the ground state and among the excited states. The lifetime of the $\text{1}{}_{\mathrm{u}}\text{(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{)}$ excimer state is calculated to be 1.4 μsec with the 335 nm band assigned to the $\text{1}{}_{\mathrm{u}}\text{→ X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ transition. The 485 nm bands cannot be assigned to any Hg₂ transitions. Strong bound-continuum absorptions are predicted for the 485 nm bands. On the other hand, the 335 nm emission is predicted to be absorbed by bound-bound transitions only.     

Extension of Rydberg absorption series of N2, A 2Πu ← X 1Σg+

Rydberg absorption series of N₂ converging to the $\text{A}{}^2\text{Π}{}_{\mathrm{u}}$ state of N₂⁺ have been reinvestigated with a 6.65-m normal incidence vacuum spectrograph in the second order. Previously known A ← X series (I) and (II) have been extended to higher members with m ～ 40 and up to v′ = 7.     

Theoretical prediction of the vertical electronic spectrum of the C2H radical

The vertical transition energies and oscillator strengths from the $\text{X}\text{?}{}^2\text{Σ}{}^{\mathrm{+}}$ ground and $\text{A}\text{?}{}^2\text{Π}$ excited states of the ethynyl radical C₂H to all higher-lying states resulting from excitation out of π and σ into $\text{π}{}^1$ and $\text{σ}{}^1$ valence-shell MO's, respectively, as well as into 3s and 3p Rydberg species, are calculated by large-scale CI techniques. It is found that the first excited states all result from $\text{π → π}{}^1$ excitations (the lowest three with quartet character), and not from the 4σ → 5σ counterparts favored in the case of isoelectronic CN. This distinction can be explained on the basis of orbital stability differences caused by the effects of hydrogen mixing. The first six states of the C₂H⁺ ion are also treated, and the correspondence with the various associated Rydberg series is discussed. Dipole moments for the $\text{X}\text{?}{}^2\text{Σ}{}^{\mathrm{+}}$ and $\text{A}\text{?}{}^2\text{Π}$ states are also calculated.     

Chemiluminescence of IF in the gas phase reaction of I2 with F2

Emission from both the state and the previously unreported $\text{A}{}^3\text{Π}{}_1$ state of IF has been observed in the gas phase reaction of I₂ with F₂ at low pressures. For the state the transition moment and vibrational populations were extracted from the spectra by a least-squares method whereby theoretical band shapes were fit to the experimental data. The effect of flow rates of reactants and Ar on the relative emission from the two electronic states, the effect of pressure on the state, and extinction of emission near 470 nm all favor the population of excited electronic states through a four-center reaction complex, rather than association of F and I atoms.It is argued that there is an avoided curve crossing between the lowest two ³Π_0⁺ states of IF, and that the ground state dissociation energy is 23 229 ± 100 cm^?1. The radiative lifetime of the state is estimated to be 10^?3 sec and to be much shorter than that of the $\text{A}{}^3\text{Π}{}_1$ state.     

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.     

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.     

Predissociation of the Schumann-Runge bands of O2

The predissociation line broadening in the Schumann-Runge bands of O₂ is interpreted through an ab initio calculation of the pertinent repulsive potential energy curves and spin-orbit matrix elements. The ab initio results provide an overall qualitative picture of the predissociation which is further refined through a detailed comparison of calculated level shifts and widths with experimental data. The position of the dominant repulsive curve is also deduced by a deperturbation of the level shift in the second vibrational difference. The predissociation is dominated by the ⁵Π_u state crossing the $\text{B}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}$ state around 1.875 Å with a spin-orbit matrix element of 65 cm^?1. The ¹Π_u and ³Π_u states have small spin-orbit matrix elements and play only minor roles in the predissociation. The calculated and experimental widths are in good agreement for low and high vibrational levels. The apparent experimental widths between v = 5 and 11 are shown to be inconsistent with the theoretical analysis, the difference probably being due to line blending.     

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 spectrum and structure of the He2 molecule: Multichannel quantum defect analyses of the triplet levels associated with (1σg)2(1σu)npλ

Emission spectra for the electronic transitions $\text{6–17pπ}{}^3\text{Π}{}_{\mathrm{g}}\text{-2s a}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ and $\text{7–16pσ}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{-2s a}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ of He₂ are reported and the electronic structures of $\text{npπ}{}^3\text{Π}{}_{\mathrm{g}}{}^{\mathrm{?}}$ and $\text{np(}{}^2\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ characterized. The energy levels associated with $\text{(1σ}{}_{\mathrm{g}}\text{)}{}^2\text{(1σ}{}_{\mathrm{u}}\text{)np(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ exhibit extensive channel mixing, which leads to a breakdown of conventional band models for the higher n¹-members of these Rydberg “series.” However, a model based on multichannel quantum defect theory quantitatively correlates the observed level structures. The higher-energy ($\text{n}{}^1\text{> ～5}$) portions of the $\text{np(}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ channels can be represented by two eigen-quantum defects μ₁ = 0.225 and μ₂ = 0.930 and the close- to loose-coupling matrix elements $\text{U}{}_{11}\text{= U}{}_{22}\text{= [N(2N + 1)}{}^{\mathrm{?1}}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{U}{}_{12}\text{= ?U}{}_{21}\text{= [(N + 1)(2N + 1)}{}^{\mathrm{?1}}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$. The inclusion of energy dependence in the μ_α's leads to quantitative correlations for all n¹-values.     

Absolute vacuum ultraviolet absorption spectra of some gaseous azabenzenes

Absolute extinction coefficient and oscillator strength of pyridine, pyrimidine, pyrazine, and s-triazine were recorded with moderate resolution in the region of 3.5–9.5 eV. Analogous to ${}^1\text{A}{}_{\mathrm{<mtext>1</mtext><mtext>g</mtext>}}\text{→}{}^1\text{B}{}_{\mathrm{<mtext>2</mtext><mtext>u</mtext>}}$, ¹B_1u, ${}^1\text{E}{}_{\mathrm{<mtext>1</mtext><mtext>u</mtext>}}\text{π → π}{}^1$ transitions of benzene, several $\text{n → π}{}^1$ and Rydberg transitions are presented and discussed.     

Spectrum and structure of the He2 molecule: Characterization of the triplet states associated with (1σg)2(1σu)nsσ, ndσ, ndπ, and ndδ (n = 5–12)

Emission spectra for the electronic transitions $\text{ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}\text{) → 2pπ b}{}^3\text{Π}{}_{\mathrm{g}}\text{(n = 5–12)}$, $\text{nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 2pπ b}{}^3\text{Π}{}_{\mathrm{g}}\text{(n = 5–12)}$, $\text{ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}\text{) → 3pσ c}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{(n = 5–10)}$, $\text{nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 3pσ c}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{(n = 5–11)}$, $\text{ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}\text{) → 3pπ e}{}^3\text{Π}{}_{\mathrm{g}}\text{(n = 6–11)}$, $\text{nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 3pπ e}{}^3\text{Π}{}_{\mathrm{g}}\text{(n = 6–11)}$, $\text{nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 4pσ g}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{(n = 9–11)}$, and $\text{10dδ}{}^3\text{Δ}{}_{\mathrm{u}}\text{→ 4pσ g}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ of ⁴He₂ are reported and the electronic structure of the triplet states associated with v = 0 of (1σ_g)²(1σ_u) nsσ and ndλ characterized. The energy levels comprising the $\text{(1σ}{}_{\mathrm{<mtext>g</mtext>}}\text{)}{}^2\text{(1σ}{}_{\mathrm{<mtext>u</mtext>}}\text{)ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{)}$ and the $\text{(1σ}{}_{\mathrm{<mtext>g</mtext>}}\text{)}{}^2\text{(1σ}{}_{\mathrm{<mtext>u</mtext>}}\text{)ndλ(}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{)}$ manifolds exhibit strong channel mixing, while the mixing of the $\text{(1σ}{}_{\mathrm{<mtext>g</mtext>}}\text{)}{}^2\text{(1σ}{}_{\mathrm{<mtext>u</mtext>}}\text{)nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ with the $\text{nd(}{}^3\text{λ}\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{)}$ channel structure is relatively minor. Models based on multichannel quantum defect theory are used to aid in the spectral assignments and to correlate the observed level structures. We show that three-limit and two-limit models adequately represent the bulk of the observed $\text{ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{)}$ and $\text{ndλ(}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{)}$ channel structures, respectively.     

Near-infrared bands of S2: 3Πgi-3Σu+ system

Vibrational and rotational analyses of the near-infrared bands of S₂ lying in the region 7440–8085 Å are reported. They form a new band system involving a ${}^3\text{Π}{}_{\mathrm{gi}}\text{-}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ transition and arise from the same initial ³Π_gi state of the ³Π_gi-³Δ_ui band system reported earlier. The analyses of the bands of this system due to the isotopic molecules ³²S³⁴S and ³⁴S₂ are also reported.