The electronic spectrum of PN. A configuration interaction study

Potential energy curves were calculated for the ground state of PN and for all excited singlet and triplet states resulting from the 2π → 3π, 7σ → 3π, 2π → 8σ, and 7σ → 8σ orbital excitations. CI studies at 4 Å served to establish dissociation energies. Spectroscopic constants were calculated, and are in good agreement with those of the known X¹Σ⁺ and A¹Π states. Overall, their similarity with those observed for N₂ is striking. Various states considered to perturb the known excitations are discussed. The recently discovered second ¹Σ⁺ state is included.     

Absorption spectra of diatomic molybdenum nitride (MoN), molybdenum oxide (MoO), and molybdenum dimer (Mo2) molecules isolated in Ar,Ne, and Kr matrices

MoN and MoO molecules produced in a hollow cathode discharge have been trapped in Ne, Ar, and Kr matrices at 4.2 and 13 K and investigated by optical spectroscopy. Bands attributed to MoN were identified in the red and blue spectral regions and assigned by comparison with gas phase results to the A⁴π → X⁴Σ^? (a) and B⁴Σ → X⁴Σ^? (a) transitions, respectively. The ground state of Mo¹⁴N has been identified as ⁴Σ^? with ω_e = 1040 cm^?1 in an Ar matrix. Absorptions assigned to MoO in the red spectral region form the (0-0) and (1-0) bands of at least one electronic transition, but could not definitely be correlated with the gas phase results. The ground state vibrational frequency for Mo¹⁶O in an Ar matrix is 893.5 cm^?1. Additionally, Mo₂ absorptions centered at 19 305 cm^?1 were shown to be part of a vibrational progression with an average spacing of 181 cm^?1.     

Rotational distribution in simultaneously excited electronic states of CH

A²Δ, B²Σ^? and C²Σ⁺ states of CH were excited in discharges through flowing C₂H₂ and C₂H₄ and in flames of C₂H₂. The rotational distributions in these states were determined from the measured integrated intensities of rotational lines for bands of A²Δ → X²Π, B²Σ^? → X²Π and C²Σ⁺ → X²Π. The A²Δ state exhibits a non-Maxwellian distribution while the B²Σ^? and C²Σ⁺ states show Maxwellian distributions. The non-Maxwellian distribution of the A²Δ state and the different rotational distributions in the three states are discussed.     

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.     

MRCI studies on ground and excited states of CBr

Potential curves and spectroscopic constants for a large number of doublet and quartet states of CBr were obtained by multireference configuration interaction calculations, using valence triple-zeta basis sets with polarization and diffuse functions. Besides the X²Π ground state, 1⁴Σ^?, 1²Δ and 2²Σ⁺ have been found to be stable. Spectroscopic constants calculated for 1²Δ are in excellent agreement with experimental values obtained by Dixon and Kroto in 1963. Their observed predissociation of one component of 1²Δ can be explained by the crossing of the 1²Δ potential near equilibrium by 1²Σ⁺. The 1²Σ⁺ state is calculated to have a shallow long-range minimum at 2.31?Å. The dissociation energy of X²Π is calculated to be 3.43?eV. An observed T _e of 4.97?eV for 2²Σ⁺ agrees with the theoretical value. Several Rydberg states of the 2π→Ryd and 3σ→Ryd series, starting at T _e ?=?5.25?eV, were identified. Photodissociation of CBr by sunlight, important in the ozone cycle, can occur via direct dissociation of the ground state, or by excitation to 1²Δ followed by predissociation. Most dissocative repulsive states lie at higher energies, and are not expected to participate in the photodisscociation of CBr.     

Diagnosis of OH radical by optical emission spectroscopy in a wire-plate bi-directional pulsed corona discharge

The emission spectrum of the molecule OH (A²Σ→X²Π, 0–0) during a high-voltage, bi-directional pulsed corona discharge consisting of a gas mixture of N₂ and H₂O in a wire-plate reactor has been successfully recorded under severe electromagnetic interference at atmospheric pressure. The relative vibrational populations and the vibrational temperature of N₂ (C, v′) have also been determined. Due to the difficulty of determining the exact overlapping spectral line shape function of the OH (A²Σ→X²Π, 0–0) and the Δv=+1 vibrational transition band of N₂ (C³Π_u→B³Π_g), a practicable Gaussian form is used for calculating the emission intensity of OH (A²Σ→X²Π, 0-0) and the Δv=+1 vibrational transition band of N₂ (C³Π_u→B³Π_g). The emission intensity of OH (A²Σ→X²Π, 0–0) has been evaluated with a satisfactory accuracy by subtracting the emission intensity of the Δv=+1 vibrational transition band of N₂ (C³Π_u→B³Π_g) from the overlapping spectra. The relative population of OH (A²Σ) has been obtained by the emission intensity of OH (A²Σ→X²Π, 0–0) and Einstein's transition probability. The influences of peak voltage, pulse repetition rate and O₂ flow rate on the relative population of OH (A²Σ) radicals have also been investigated. We found that the relative population of OH (A²Σ) rises with an increase in both the peak applied voltage and the pulse repetition rate. When oxygen is added to an N₂ and H₂O gas mixture, the relative population of OH (A²Σ) radicals decreases exponentially with an increase in added oxygen. The main physicochemical processes involved are also discussed in this paper.     

Partial-wave analysis of backwardly produced three-pion systems in K−p interactions at 4.2 GeV/c

We report on the results of a partial-wave analysis of the 3π system produced by baryon exchange in the reaction K^?p→Σ^?π⁺π⁺π^? at 4.2 GeV/c. We confirm the existence of an enhancement in the 1⁺S(?π) wave as previously established from a Dalitz plot analysis of the same data. The phase variation of this wave is found to be consistent with that expected for a resonance and thus the enhancement is identified with A₁ production. No clear signal for this state is found in either the reaction K^?p→Σ⁺π⁺π⁺π^?π^? or K^?p→Λπ⁺π^?π⁰. We also find production via baryon exchange of the A₂ in all three reactions and the ω and $\text{ω}{}^1$ (1975) in the third reaction.     

Backward production of a spin parity 1+ϱπ enhancement at 1.04 GeV

A spin-parity 1⁺?π enhancement is observed for the 3π mass spectrum in the reaction K^?p → Σ^?π⁺π⁺π^? where events with a small (K^? → Σ^?) momentum transfer are selected. The mass (1040 MeV) and width (230 MeV) of this enhancement are reminiscent of the A₁ → ?π bump which has mainly been observed in the diffractive-like processes. The cross section for this enhancement at 4.15 GeV/c incident K^? momentum is (3.6 ± 0.5) μb.     

Investigation of N 2 + (C 2Σ u + → X 2Σ g + fluorescence excited through auger decay of the 1s −1π* resonance

A theoretical investigation of N ₂ ⁺ (C ²Σ _u ⁺ → X ²Σ _g ⁺ molecular fluorescence excited through the Auger decay of the 1s ^?1π* resonance is carried out. The fluorescence cross sections are calculated with due regard for the dependence of the matrix element of the C → X dipole transition on the internuclear distance, the interference between channels of excitation via different vibrational levels v _r of the 1s ^?1π* resonance, the rotational structure of the fluorescence band, and the predissociation of the N ₂ ⁺ C ²Σ _u ⁺ v′ ≥3) states. The calculated cross sections are in good agreement with the experimental results of recent measurements. The results of the calculations have demonstrated that the observed dependence of the cross section of the (C ²Σ _u ⁺ (v′) → X ²Σ _g ⁺ (v″) fluorescence on the excitation energy and the fluorescence wavelength for a group of bands with equal values of the difference Δv = v′ ? v″ is associated with transitions between the vibrational levels of the electronic states involved in the excitation and subsequent cascade decay of the 1s ^?1π* resonance: N₂ (v ₀ = 0) → N*₂(1s ^?1π*(v _r)) ? N ₂ ⁺ : (C ²Σ _u ⁺ (v′) → X ²Σ _g ⁺ (v″).     

The B2Σ+ → A2Πi system of silicon nitride,SiN

The 440-nm violet-degraded ${}^2\text{Σ →}{}^2\text{Π}$ bands of SiN, which were previously assigned to a $\text{“K” → A}$ system, have been reanalyzed. These bands are shown to be Δv = 0, ±1 sequence bands of the B²Σ⁺ → A²Π system of SiN. The first reliable value of T_e(A²Π) = 994.4(1) cm^?1 has been obtained, and this determines the location of the D²Π and L²Π states with respect to the ground state. The B²Σ⁺, v = 7 and D²Π, v = 3 levels are shown to be mutually perturbing. A detailed study has been made of the perturbed X²Σ⁺, v = 8 level. The 6–8 band of the B → X system has been photographed at high resolution. A deperturbation of this band confirms T_e(A²Π), and provides the first experimental verification of the inverted nature of the A state.     

A global potential energy surface for H2S+(X 4A′′) and quasi-classical trajectory study of the S+(4S) + H2(X1Σ+g) reaction

A novel global potential energy surface for H₂S⁺(X?⁴A″) based on accurate ab initio calculations is presented. Energies are calculated at the multi-reference configuration interaction level with Davidson correction using aug-cc-pVQZ basis set plus core-polarisation high-exponent d functions. A grid of 4552 points is used for the least-square fitting procedure in the frame of a many-body expansion. The topographical features of the new potential energy surface are here discussed in detail. Such a surface is then employed for dynamic studies of the S(⁴S) + H₂(X?¹Σ⁺_g) →SH⁺(X?³Σ^?) + H(²S) reaction using the quasi-classical trajectory method. State specific trajectories are calculated, for both ground and ro-vibrationally excited initial states of H₂(X?¹Σ⁺_g). Corrections to the zero point energy leakage of the classical calculations are also presented. Calculated reaction cross sections and rate constants are here reported and compared with available literature.     

Theoretical studies on 14 Λ-S and 30 Ω states of BeBr molecule: potential energy curves,spectroscopic parameters and spin–orbit couplings

Using the complete active space self-consistent field (CASSCF) method followed by the internally contracted multi-reference configuration interaction (MRCI) approach in combination with the correlation-consistent basis sets, this paper studies the potential energy curves of X²Σ⁺, 2²Σ⁺, 3²Σ⁺, 1²Σ^?, A²Π, 2²Π, 3²Π, 1²Δ, 1⁴Σ⁺, 2⁴Σ⁺, 1⁴Σ^?, 1⁴Π, 2⁴Π and 1⁴Δ Λ-S states of BeBr molecule and the corresponding 30 Ω states for the first time. All the Λ-S states correlate to the first two dissociation channels, Be(¹S_g) + Br(²P_u) and Be(³P_u) + Br(²P_u), of BeBr molecule. Of these Λ-S states, the 3²Π and 2⁴Π are found to be repulsive without the spin–orbit coupling, whereas 1⁴Π, 2⁴Π, 3²Π and 2⁴Σ⁺ are found to be repulsive with the spin–orbit coupling included. A²Π and 2²Σ⁺ possess the double well whether the spin–orbit coupling effect is included or not. Only 1⁴Σ⁺, 1⁴Σ^?, 1²Π and 2²Π are found to be the inverted Λ-S states. The spin–orbit coupling is accounted for by the state interaction approach with Breit–Pauli Hamiltonian using the all-electron cc-pCVTZ basis set. The potential energy curves determined by the internally contracted MRCI method are corrected for size-extensivity errors by means of the Davidson correction. Core–valence correlation correction is calculated with a cc-pCVTZ basis set. Scalar relativistic correction is included using the third-order Douglas–Kroll Hamiltonian approximation at the level of cc-pVTZ basis set. The spectroscopic parameters of all the Λ-S and Ω bound states are evaluated. The spectroscopic parameters are compared with those reported in the literature. Fair agreement is found between the present results and available measurements. In particular, the energy splitting of 204.43 cm^?1 in the A²Π Λ-S state agrees well with the measurements of 201 cm^?1. Analyses demonstrate that the spectroscopic parameters reported here can be expected to be reliably predicted ones.     

Electron-vibrational energy exchange in collisions of electronically excited N2(A 3Σ u + ) molecules with Zn(X 1 S) atoms

The interaction matrix between the N₂ molecule in the X ¹Σ _g ⁺ and A ³Σ _u ⁺ states and the Zn atom in the ¹ S and ³ P states calculated earlier by the asymptotic method was used to find the rate constants for the electron-vibrational energy exchange N₂(A ³Σ _u ⁺ , v) + Zn(¹ S) → N₂(X ¹Σ ₈ ⁺ , v′) + Zn(³ P). The calculations were performed by the transition state method, and the probabilities of transitions between intersecting electron-vibrational terms of the system in motion along the reaction coordinate were determined by the Landau-Zener equation. The calculated electron excitation transfer constants between N₂(A ³Σ _u ⁺ , v = 1, 0) and Zn(¹ S) over the temperature range 300–900 K were on the order of 10^?11?10^?12 cm³/s.     

Phase-shift analysis of π N → K Σ

We have performed an energy-independent phase-shift analysis of πN → KΣ by analyzing differential cross-section and polarization data for the reactions π⁺p → K⁺∑⁺ and

at fifteen energies from threshold to 2137 MeV invariant mass. The single-energy solutions were linked by shortest-path methods with and without constraints implied by the Odorico zeros for the reaction π^?p → K⁺Σ^?. Similar to π^?p → KΛ it has been found that both isostates are dominated below 1900 MeV by resonances in the spin $\text{1}\text{2}$ waves. The F₃₇ resonance couples to KΣ with √x_πNx_KΣ= 0.04.     

Accurate theoretical spectroscopic investigations of the 20 Λ-S and 58 Ω states of O2+ cation including the spin–orbit coupling effect

The potential energy curves (PECs) are calculated for the 20 Λ-S states (X²Π_g, A²Π_u, B²Σ^?_g, a⁴Π_u, b⁴Σ^?_g, b′⁴Π_g, c⁴Σ^?_u, 1²Σ⁺_g, 1²Σ⁺_u, 1²Σ^?_u, 1⁴Σ⁺_g, 1⁴Σ⁺_u, 1⁴Δ_g, 1⁴Δ_u, 1⁶Σ⁺_g, 1⁶Σ⁺_u, 1⁶Π_g, 1⁶Π_u, 2⁴Π_g and 2⁴Π_u) of O₂⁺ cation and their corresponding 58 Ω states. Of these 20 Λ-S states, the 1⁶Π_u state is found to be repulsive. The 1²Σ⁺_g, 1⁴Σ⁺_u, c⁴Σ^?_u and 1⁴Δ_u states are found to possess the double well. The b⁴Σ^?_g, 1⁶Σ⁺_g, 1⁴Σ⁺_u, a⁴Π_u, A²Π_u, 1⁶Π_g and 2⁴Π_g states are found to be inverted with the spin–orbit coupling effect included. The b′⁴Π_g, 1⁶Π_g, 1⁶Σ⁺_g, 1⁴Σ⁺_u and 1⁴Δ_u states, and the second well of the 1²Σ⁺_g state are found to be the weakly bound states. The b′⁴Π_g state is found to possess one well with one barrier. The PECs are calculated by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson correction in combination with the aug-cc-pV6Z basis set. The core–valence correlation and scalar relativistic corrections are included. The convergent behaviour of present calculations is discussed with respect to the basis set and theoretical level. The spin–orbit coupling effect is accounted for. The PECs are extrapolated to the complete basis set limit. The spectroscopic parameters are evaluated, and compared with available measurements. It demonstrates that the spectroscopic parameters reported here can be expected to be reliably predicted ones.     

The Hg2 (A3Ou− → X1Σg+) and (A31u → X1Σg+) fluorescence

The fine structure emission sepctrum near 5500 Å attributed to the Hg₂ (A³O_u^? → X¹Σ_g⁺) transition is shown to be strikingly similar to the HgCl (B²Σ⁺ → X²Σ⁺) emission spectrum sensitized by Hg(6³P_o) metastables. The correct Hg₂ (A³O_u^? → X¹Σ_g⁺) emission spectrum at 4850 Å was re-examined and confirmed to be a continuous one. It is suggested that the fine structure arose from the sensitization of a chlorine containing impurity.     

Pressure shift and/or broadening of lines in the electronic spectra of Cl2, Br2, I2, O2, HD,AlH and H2CO

Line positions and widths of the B³Π_o⁺u?X¹Σ⁺_g electronic transitions of chlorine and bromine gases are measured in absorption as functions of pressure by means of a scanning Fabry-Perot interferometer spectrometer (resolving power > 10⁶). No dependences on quantum numbers are detected. Deconvolutions of measured full-widths-at-half-maxima (FWHM) reveal collision broadening for pressures between 1 and 225 torr. The ratio of self-broadening to shift is always less than that expected for a van der Waals interaction in the impact approximation, namely -2.77. Accordingly, the Lennard-Jones potential is used to determine the effect of the electronic transitions on C₆ and C₁₂, and there are found 14 and 6% changes in C₆ for Cl₂ and Br₂, respectively. If, instead, one uses the self-broadening only, and a pure van der Waals interaction, the changes are 6 and 5%. Because the effects are in either model unexpectedly small, comparisons are made with less complete measurements (from the literature) for self-broadening in I₂, the B¹Σ⁺_g?X³Σ^-_g system of O₂ and the B^′Σ⁺_g?X¹Σ⁺_g system of HD, and for foreign-gas broadening in the A¹Π?X¹Σ system of A1H and the A̋¹A₂(π¹, n)?X̋¹A₁ system of H₂CO as well as the HD system.     

Transition probabilities of the X1Σ+, A1Π, B1Δ, C1Σ+, and D1Π states of the AlO+ cation

ABSTRACT

This study computes the potential energy curves of the X¹Σ⁺, A¹Π, B¹Δ, C¹Σ⁺, and D¹Π states of AlO⁺ cation and the transition dipole moments between them. The orders of the rotationless radiative lifetimes are 10–100?μs for the A¹Π state, 1–1000?ms for the B¹Δ state, 10?ns for the first well and 100?ns for the second well of the C¹Σ⁺ state, and 1?μs for the D¹Π state. Emissions of the B¹Δ–A¹Π and D¹Π–C¹Σ⁺ systems are so weak that they are hardly measured via spectroscopy, the emissions of the C¹Σ⁺–X¹Σ⁺, C¹Σ⁺–A¹Π, and D¹Π–X¹Σ⁺ systems are so strong that they can be detected readily, and emissions of the A¹Π–X¹Σ⁺ and D¹Π–A¹Π systems can be observed through spectroscopy only by a significant effort. There is a strong great similarity between spontaneous emissions of the A¹Π–X¹Σ⁺ system of the AlO⁺ cation and the A²Π–X²Σ⁺ system of the AlO radical. The emissions of the A²Π–X²Σ⁺ system of the AlO radical have been measured in outer space Therefore, it is highly possible that the emissions of the A¹Π–X¹Σ⁺ system of the AlO⁺ cation can be detected in the astrophysical media.     

Analysis of Dissociation—Recombination Processes for the CO<Subscript>2</Subscript> Molecule with the Spin—Orbit Coupling Taken into Account

The dissociation CO₂(X¹Σ) + M → CO(X¹Σ) + O(³P) + M and recombination CO(X¹Σ) + O(³P) + M → CO₂(X¹Σ) + M processes are considered with the spin—orbit coupling taken into account in the ground and several excited states of the CO₂ molecule. Because of the specific features of mutual position of potential energy surfaces of the CO₂ molecule in the ground and several excited states and the large values of spin—orbit interaction matrix elements, which causes the quantum nonadiabatic transition of the molecule from one state to another, these processes become effectively spin-allowed and the rate constants for the nonadiabatic reactions have large values. The proposed dissociation and recombination mechanisms include reactions involving singlet—triplet crossings.