The electronic spectrum of silicon monotelluride radical

In the electronic spectrum of silicon monotelluride which has been produced in microwave discharges through sealed tubes, a large number of new bands belonging to theA ¹Π-X ¹Σ⁺ system (3100–3900 Å) and theE ¹Σ⁺-X ¹Σ⁺ system (2800–3100 Å) of Si¹³⁰Te has been observed. The vibrational structure analyses of these band systems have resulted in the determination of improved vibrational constants in all the three electronic states involved in these transitions. An error in the previous determination of the vibrational constants of theE ¹Σ⁺ state has been corrected. An upper limit for the dissociation energy of the silicon monotelluride has been determined to be 40,000 cm^?1.     

Extension of the A1Σ+-X1Σ+ system of7LiH near the dissociation limit

The absorption spectra of⁷LiH have been photographed in the 3,500?2,900 Å region using the second order of a 3.4 M Ebert spectrograph. Observations comprise previously observedA ¹ Σ ⁺-X ¹ Σ ⁺ transitions and several new vibrational bands of this system near the ionisation limit. Rotational and vibrational analysis of these bands (16≦V′≦20) have been carried out and the rotational constants for the upper states have been determined.     

Spectroscopic studies of the sulphur afterglow

The afterglow emission spectrum of sulphur and argon mixture is found to consist of (a) the main band system of S₂(B³Σ^-_u?X³Σ^-_g) in the region 3200–6600 Å and (b) the atomic spectrum of argon in the 7500–9000 Å region. Although B?X bands of S₂ obtained by ordinary excitation extends from 2829 to 7100 Å, the lower wavelength limit of these bands from the afterglow is only 3200Å. It is proposed that the S₂ molecules are formed in the B³Σ^-_u state through inverse predissociation when two S atoms approach each other along the potential curve of the predissociating electronic state 1_u.     

The optical spectrum of the doubly charged molecular nitrogen ion: Rotational analysis of the (0-0) and (1-1) bands of the D1Σu+-X1Σg+ transition of N22+: Comparison of observations with Ab-initio calculation results

Emission spectra obtained in the 1550–1650 Å region with a 10-m vuv spectrograph are conclusively assigned to the N₂²⁺ ion. The 1589-Å band, previously observed by Carroll, and a new band of the same system, have been rotationally analyzed. Ab-initio calculations have been performed which support the assignment of these two bands to the D¹Σ_u⁺-X¹Σ_g⁺ system. The calculations also explain the observed breaking-off points in the branch structure as well as weakening and broadening of the other expected bands. These phenomena arise from electron configuration changes and perturbation effects in the ground state.     

Rotational analysis of the a3Π-X1Σ+ bands of GaD

A new method of producing strong and clean emission spectra of the gallium hydride/deuteride molecule has been developed. Five bands belonging to the gallium deuteride molecule (GaD) have been photographed under high resolution. The rotational analyses of the bands lying at 5669.14 Å (0-0) and 5675.10 Å (1-1) in the a³Π₁-X¹Σ⁺ transition, 5761.0 Å (0-0) and 5766.20 Å (1-1) in the a³Π_0⁺-X¹Σ⁺ transition, and 5760.85 Å (0-0) in the a³Π_0⁻-X¹Σ⁺ transition have been performed. Accurate rotational constants (B, D) have been determined for the X¹Σ⁺, a³Π_0^± and a³Π_1^± states. The Λ doubling in the a³Π₀ (v = 0) and a³Π₁ (v = 0 and 1) states are obtained.     

The electronic spectrum of bismuth monofluoride: An 0+ ← X10+ band system at 3838 Å

Emission bands of BiF (in the region of 3800 Å), formerly designated as belonging to the B-X₁0⁺ and A₃-X₁0⁺ transitions, have been photographed and rotationally analyzed under high resolution. These bands have been found to belong to an 0⁺ ← X0⁺ system. Extensive rotational and vibrational perturbations have been observed and the nature of the perturbing state is discussed.     

The spectra of YF+ and YF molecules in the 3400–3700 Å region

The violet-degraded band system (3400–3700 Å) has been found in the spectrum of a discharge through helium with a trace of YF₃ vapor. The emitter of this system is the hitherto unknown YF⁺ ion. Vibrational analysis of the band system has been carried out. Rotational analysis has shown that the bands are due to the ²Π-²Δ transition. Molecular orbital configurations which give rise to both participating states are discussed. The ¹Σ-X¹Σ (0-0) band of YF (λ3572 Å) obtained in absorption has been reanalyzed.     

Reexamination of the vacuum ultraviolet emission spectrum of CO in the 950–1200 Å region

New spectrograms of CO below 1200 Å reveal that emission bands terminating on the high energy $\text{E}{}_0{}^1\text{Σ}{}^{\mathrm{+}}$ and ¹Π states plus most of the previously reported unidentified emission bands of CO actually originate from molecular nitrogen. Four new emission band systems in CO, tentatively identified as V¹Π-X¹Σ⁺, W¹Π-X¹Σ⁺, Y¹Σ⁺-X¹Σ⁺, and Z¹Σ⁺-X¹Σ⁺, have been observed. The corresponding T_v0′s are 98917, 102804, 99963, and 105724 cm^?1, respectively.     

The RKR potential energy curves for the X1Σ+ and A1Σ+ states of RbH

The A¹Σ⁺-X¹Σ⁺ laser-excited fluorescence spectrum of RbH was observed in the 4760-to 8470-Å region, using the Ar⁺ 4765-Å exciting line, and v″ = 6–12 were observed for the first time. New spectroscopic constants were obtained for the X¹Σ⁺ and A¹Σ⁺ states of RbH. New Rydberg-Klein-Rees (RKR) potential energy curves were calculated up to v″ = 12 of the X¹Σ⁺ state and up to v′ = 14 of the A¹Σ⁺ state.     

The laser-induced fluorescence of IBr79

Four fluorescence progressions of the B0⁺-X¹Σ⁺ band of IBr⁷⁹ excited by a single-mode cw dye-laser have been observed and analyzed. Discrepancies in the reported rotational constants of the ¹Σ⁺ state have been resolved and improved vibrational constants determined. A simple method of discriminating between IBr and interfering I₂ fluorescence is described.     

New spectroscopic analyses and potential energy curves for the X1Σ+ and A1Σ+ states of NaH

The emission spectrum of NaH has been photographed in the ～6000–7300-Å region. Additional bands of the A¹Σ⁺ electronic transition have been analyzed and in particular the observed vibrational structure of the excited A state has been extended down to v′ = 0. New spectroscopic constants have been obtained, the v′ = 0 data leading to especially large changes in the constants of the anomalous A¹Σ⁺ state. New Rydberg-Klein-Rees (RKR) potential energy curves have been calculated up to v″ = 8 of the X¹Σ⁺ state and up to v′ = 20 in the A¹Σ⁺ state.     

The 1Σ+-X1Σ+ transition of the PN molecule

The recently observed ¹Σ⁺-X¹Σ⁺ transition of the PN molecule (J. Phys. B.13, 2251–2254 (1980)) has been photographed at high dispersion in the 1600–1900-Å region. A rotational analysis is carried out and shows 11 vibrational levels of the new ¹Σ⁺ state. These levels are perturbed and absolute vibrational numbering cannot be determined. Some perturbations can be accounted for by interactions with the A¹Π state. Weakening of lines are explained as accidental predissociations and allow us to discuss the dissociation energies of the X¹Σ⁺ and A¹Π states.     

The A 1Σ+ → X 1Σ+ bands of the isotopic lithium hydrides

In order to obtain a better understanding of the X¹Σ⁺ ground state and the A¹Σ⁺ state potential energy curves of lithium hydride and to examine in detail the concept of “mass-reduced quantum numbers” for both an ordinary (X¹Σ⁺) and an anomalous (A¹Σ⁺) electronic state, the emission spectra of the A¹Σ⁺ → X¹Σ⁺ bands of the isotopic lithium hydrides and deuterides were photographed in the 3000–5000-Å region with a 3.4-m Ebert Spectrograph. The bands found involved v″ = 0 to 7 to various v′ = 0 to 17 for ⁶LiH, and v″ = 0 to 7 to various v′ = 1 to 16 for ⁶LiD. Additional bands involving v″ = 4 and 5 were also found for ⁷LiH. The vibrational-rotational spectroscopic analysis of ⁷LiH, ⁶LiH, and ⁶LiD are reported here, as are the reanalyses of the ⁷LiH and ⁷LiD data reported by Crawford and Jorgensen. New Rydberg-Klein-Rees (RKR) A¹Σ⁺ and X¹Σ⁺ potential curves have been constructed for each individual molecule and are reported, but detailed isotopic comparisons will be reported in subsequent publications.     

The A3Π(1) → X1Σ+ emission spectrum of ICl in the near infrared: Rotational analysis of bands in the v′ = 0, 1, 2, 3, 4, progressions and molecular constants for the X1Σ+ and A3Π(1) states by merging with absorption data

Ten bands of the A³Π(1) → X¹Σ⁺ emission system of I³⁵Cl, lying at wavelengths of 8180 – 10000 Å, have been analyzed rotationally in the ranges 0 ≤ v′ ≤ 4 and 6 ≤ v″ ≤ 9. Constants determined from least-squares fits of frequencies of individual bands are merged with constants derived from absorption data. RKR potentials for both states are reported, and the Franck-Condon factors for ICl (A-X) have been computed for 0 ≤ v′ ≤ 35 and 0 ≤ v″ ≤ 9.     

Electronic spectra and structure of the hydrogen halides: States associated with the (σ2π3)cσ and (σ2π3)cπ configurations of HI and DI

The high resolution absorption spectra of HI and DI have been investigated in the ～ 1425 Å to 1570 Å region. The majority of the bands observed in the region are assigned to transitions from X¹Σ⁺ to states associated with the excited configurations (σ²π³)cσ and (σ²π³)cπ. This region also contains bands assigned to transitions from X¹Σ⁺ to states associated with more highly excited configurations and to excited vibrational levels of the V¹Σ⁺, b²Π, and C¹Π states. The states associated with the (σ²π³)cσ and cπ configurations exhibit $\text{Ω}$, ω coupling. Effective molecular constants are presented for the bands observed within the above wave-length region.     

Visible and near infrared emission spectra of PCl excited in the reaction of Ar(3P2, 0) with PCl3: Vibrational analysis of PCl A3Π → X3Σ− and b1Σ+ → X3Σ−

Two band systems of PCl, A³Π_r → X³Σ^? and b¹Σ⁺ → X³Σ^?, have been observed from the reaction of $\text{Ar}\text{(}{}^3\text{P}{}_{\mathrm{2,\; 0}}\text{)}$ with PCl₃ at pressures of 1–2 Torr. Seventy-eight bands of P³⁵Cl and 31 bands of P³⁷Cl in the region 4000–6000 Å have been assigned to the A³Π_r → X³Σ^? system and include levels with v′ = 0, 1, 2 and v″ = 3–18. The ground state numbering was obtained from a study of the vibrational isotope effect. The (0,0) sequence of the b¹Σ⁺ → X³Σ^? system occurs near 8200 Å and has been observed up to v′ = 10. Vibrational constants for all three states are derived from least-squares fits of the measured bandhead wavenumbers. The A ← X absorption system of PCl reported by Basco and Yee in flash photolysis of PCl₃ was not observed, and is probably due to absorption to a Rydberg state of PCl.     

An emission spectrum of InCl+

A spectrum, found in the 360- to 420-nm region following hollow-cathode excitation of InCl₃/In/He mixtures has been attributed to the InCl⁺ ion. Sixteen bands have been classified for the system which has been identified through rotational analysis to be B²Σ-X²Σ, consistent with photoelectron observations by Berkowitz and Dehmer. A second, very much weaker set of bands has been observed between 320 and 335 nm under the same experimental conditions. These latter bands constitute either a new system of InCl or a second InCl⁺ system.     

Photo-absorption studies on carbonyl sulphide in 30,000–91,000 cm−1 region using synchrotron radiation

Photo-absorption spectrum of carbonyl sulphide (OCS) is recorded in 30,000–91,000 cm^?1 (3300–1050 Å) region at an average resolution of 1.2 Å using Photo-physics beamline on the 450 MeV Indus-1 synchrotron radiation source at RRCAT Indore, India. Owing to significant absorption cross section dependence, spectra of OCS are recorded at various pressures (0.001–5 mbar) to optimize the S/N ratio for band systems appearing at different energy regions. The spectral region below 70,000 cm^?1 has contributions from dissociation mechanism of the ground state of OCS and three valence band systems arising from promotion of a 3π electron to 4π and 10σ orbital. Improved S/N ratio helped in unambiguous assignment of the valence band progressions at 42,000–48,000 cm^?1, 53,000–62,000 cm^?1 and 63,500–70,000 cm^?1 regions to the ¹Δ←X¹Σ⁺ transition, the relatively intense and sharp bands of ¹Π←X¹Σ⁺ transition and intense but broad bands of ¹Σ⁺←X¹Σ⁺ transition, respectively, and obtain the vibrational frequencies. Above 70,000 cm^?1 Rydberg series arising from s, p, d and f orbitals converging to the ionic ground state X²Π of OCS⁺ (90,121 cm^?1) are identified. Long progression in the first few members of the Rydberg series is suggestive of mixed valence character. Quantum defects are evaluated and used to discuss the nature of the molecular orbital. The present study provides a unifying picture of the VUV photo-absorption spectrum of OCS up to its first ionization limit.     

A photoelectron spectroscopic study of the second ionisation of the CF(X2Π) radical

The CF(X²Π) radical has been re-investigated with vacuum ultraviolet photoelectron spectroscopy. Two bands were observed and assigned to the ionisations CF⁺(X¹Σ⁺)←CF(X²Π) and CF⁺(a³Π)← CF(X²Π). The first band, which has been observed previously, has an adiabatic ionisation energy of (9.11±0.02) eV and a vertical ionisation energy of (9.55±0.02) eV. For the second band, three vibrational components were observed with the first, the most intense, at an ionisation energy of (13.94±0.02) eV. Analysis of the vibrational structure in the two observed bands allowed ω_e and r_e to be determined as 1810±30 cm⁻¹ and 1.154±0.005 Å, respectively for the first ionic state, CF⁺(X¹Σ⁺), and 1614±30 cm⁻¹ and 1.213±0.005 Å, respectively for the second ionic state, CF⁺(a³Π). Comparison of the ionisation energies and spectroscopic constants obtained has been made with values obtained from recent multi-reference configuration interaction calculations.