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.     

Low-lying electronic states of BeH+ with the effect of inner electrons

The potential energy curves of the low-lying electronic states of BeH⁺ molecular ion are performed by using highly accurate multi-reference configuration interaction with AV5Z basis sets for H atom and ACV5Z basis set for Be atom, 1s inner shell of Be is considered as the core orbit and the active orbit, respectively, which are used to characterise the spectroscopic properties of a manifold of singlet and triplet states. Fourteen electronic states correlated with eight dissociation channels are investigated, we have found that the a³Σ⁺ and c³Σ⁺ both are bound states, the 3³Σ⁺ possesses double wells, and the C¹Σ⁺, 3³Σ⁺, 2³Π, 2¹Π, 1¹Δ, 1³Δ, 2³Δ and 2¹Δ states are studied for the first time. Transition dipole moment, Franck–Condon factors q_υ′υ^″ and Einstein coefficients A_υ′υ^″ for A¹Σ⁺–X¹Σ⁺, 2¹Π–B¹Π, c³Σ⁺–a³Σ⁺ and b³Π–a³Σ⁺ systems have been calculated. Radiative lifetime of A¹Σ⁺–X¹Σ⁺ band system has also been determined.     

Einstein A coefficients and absolute line intensities for the E2Π–X2Σ+ transition of CaH

Einstein A coefficients and absolute line intensities have been calculated for the E²Π–X²Σ⁺ transition of CaH. Using wavefunctions derived from the Rydberg–Klein–Rees (RKR) method and electronic transition dipole moment functions obtained from high-level ab initio calculations, rotationless transition dipole moment matrix elements have been calculated for all 10 bands involving v′=0,1 of the E²Π state and v″=0,1,2,3,4 of the X²Σ state. The rotational line strength factors (Hönl–London factors) are derived for the intermediate coupling case between Hund's case (a) and (b) for the E²Π–X²Σ⁺ transition. The computed transition dipole moments and the spectroscopic constants from a recent study [Ram et al., Journal of Molecular Spectroscopy 2011;266:86–91] have been combined to generate line lists containing Einstein A coefficients and absolute line intensities for 10 bands of the E²Π–X²Σ⁺ transition of CaH for J-values up to 50.5. The absolute line intensities have been used to determine a rotational temperature of 778±3 °C for the CaH sample in the recent study.     

Photoionization studies of the atmospherically important species N and OH at the Elettra synchrotron radiation source

In this paper angularly resolved photoelectron spectra (PES) and constant-ionic-state (CIS) spectra are presented for the atmospherically important species N and OH.The natural width Γ, line shape parameters q and ρ² and discrete oscillator strengths f have been measured for the members of the N*[2s2p³(⁵S), np] (⁴P) ← N(⁴S) autoionizing resonances for n = 5–10. The n = 5 parameters calculated in this work are in good agreement with the values obtained previously whereas for the resonances with n = 6–10 the values of these parameters are reported for the first time. The asymmetry parameter (β) for the first band of N atoms, the N⁺(³P) ← N(⁴S) ionization, has also been measured in the photon energy range of the above autoionizing resonances.For OH, CIS spectra have been recorded for the first photoelectron band corresponding to the ionization OH⁺(X³Σ⁻, v⁺ = 0) ← OH(X²Π, v″ = 0). In these spectra, rotationally partially resolved bands associated with OH*(a¹Δ3d, v′ = 0) ← OH(X²Π, v″ = 0) resonances have been observed. Suggestions for their assignment are made on the basis of their positions and band simulations which use rotational line strength calculations.     

New experimental study and theoretical model of the extreme UV absorption spectrum of CO isotopologs

A review of the ¹Π–X¹Σ⁺ transitions observed in the extreme ultra violet spectra from 92 000 to 105 500 cm^?1 of four CO isotopologs is presented. It is based both from previous and new experiments. A theoretical model is suggested to assign all the ¹Π observed levels in terms of four Rydberg states interacting with the E′ ¹Π valence state. This is made by solving a set of five coupled Schrödinger equations. The agreement between theory and experiment is reasonable.     

Multibubble sonoluminescence as a tool to study the mechanism of formic acid sonolysis

Sonoluminescence spectra collected from 0.1 to 3.0 M aqueous solutions of formic acid sparged with argon show the OH(A²Σ⁺−X²Π_i) and C₂(d³Π_g → a³Π_u) emission bands and a broad continuum typical for multibubble sonoluminescence. The overall intensity of sonoluminescence and the sonochemical yield of HCOOH degradation vary in opposite directions: the sonoluminescence is quenched while the sonochemical yield increases with HCOOH concentration. By contrast, the concentration of formic acid has a relatively small effect on the intensity of C₂ Swan band. It is concluded that C₂ emission originates from CO produced by HCOOH degradation rather than from direct sonochemical degradation of HCOOH. The intensity of C₂ band is much stronger at high ultrasonic frequency compared to 20 kHz ultrasound which is in line with higher yields of CO at high frequency. Another product of HCOOH sonolysis, carbon dioxide, strongly quenches sonoluminescence, most probably via collisional non-radiative mechanism.     

Line-shape of the vibrational bands of the CN- UV emission spectra in alkali halide-cyanide mixed crystals

Measurements of the line-width of the vi$\text{b}$rational bands associated to the a³Π→X¹Σ⁺ electronic transition of the CN ion in alkali halide-cyanide mixed crystals at 2K–250K have been performed. It is obtained that the a³Π→X¹Σ⁺ electronic transition is coupled to a dominant mode of 110 cm^-1 with strength 1.2 in KCN_0.01C?_0.99. From the line-shape of the vibrational bands in all crystals at 4.2K it is suggested that this mode can be ident$\text{i}$fied with a breathing mode of the neighbouring alkali ions.     

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.     

On the spin and hyperfine splittings in the X2Σ+ ground states of AlO and AlS

A re-analysis of the A′²Π_i–X²Σ⁺ band system of the AlS radical has been performed. The previously published material has been refined and extended to approximately 36,000 line assignments. The line material has been fitted to a ²Σ⁺ hyperfine Hamiltonian, in the same manner as in the recently published work on the B²Σ⁺–X²Σ⁺ and A²Π_i–X²Σ⁺ systems of AlO. The present analysis shows the same trends for the ground state γ-values as in AlO, i.e. decreasing γ-values upon increasing v. It has been confirmed that the spin splittings of the X²Σ⁺ (v = 0) levels in both molecules are mainly due to nuclear hyperfine interaction and second order spin–orbit effects due to the high-lying regular ²Π state (C²Π in AlO and B²Π in AlS), while the influence of the low-lying inverted ²Π state on γ increases dramatically with increasing v, resulting in negative γ-values starting from v = 2.     

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.     

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.     

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.     

Near-infrared LIF spectroscopy of HfF

The molecular ion HfF⁺ is the chosen species for a JILA experiment to measure the electron electric dipole moment (eEDM). Detailed knowledge of the spectrum of HfF is crucial to prepare HfF⁺ in a state suitable for performing an eEDM measurement [1]. We investigated the near-infrared electronic spectrum of HfF using laser-induced fluorescence (LIF) of a supersonic molecular beam. We discovered eight unreported bands, and assign each of them unambiguously, four to vibrational bands belonging to the transition [13.8]0.5 ← X1.5, and four to vibrational bands belonging to the transition [14.2]1.5 ← X1.5. Additionally, we report an improved measurement of vibrational spacing of the ground state, as well as anharmonicity ω_ex_e.     

High resolution emission spectroscopy of the E2Π–X2Σ+ transition of SrH and SrD

Emission spectra of SrH and SrD have been studied at high resolution using a Fourier transform spectrometer. The molecules have been produced in a high temperature furnace from the reaction of strontium metal vapor with H₂/D₂ in the presence of a slow flow of Ar gas. The spectra observed in the 18 000–19 500 cm^?1 region consist of the 0–0 and 1–1 bands of the E²Π–X²Σ⁺ transition of the two isotopologues. A rotational analysis of these bands has been obtained by combining the present measurements with previously available pure rotation and vibration–rotation measurements for the ground state, and improved spectroscopic constants have been obtained for the E²Π state. The present analysis provides spectroscopic constants for the E²Π state as ΔG(½) = 1166.1011(15) cm^?1, B_e = 3.805503(32) cm^?1, α_e = 0.098880(47) cm^?1, r_e = 2.1083727(89) Å for SrH, and ΔG(½) = 839.1283(23) cm^?1, B_e = 1.918564(15) cm^?1, α_e = 0.034719(23) cm^?1, r_e = 2.1121943(83) Å for SrD.     

Observation of the c3Πu-X1Σg+ intersystem transition in the absorption spectrum of P2

The observation of the c³Π_u-X¹Σ_g⁺ intersystem transition of P₂ is reported. The 6-0 band of the system was identified on high resolution absorption plates teken on the NRC 10-m vacuum spectrograph at Ottawa. A rotational analysis of the band is given together with that of the adjacent 5-0 band of the C¹Σ_u⁺-X¹Σ_g⁺ system, the upper level of which is involved in a mutual perturbation with the c³Π_u, v = 6 level. The interaction parameters for the perturbation are derived. It is proposed that the appearance of the 6-0 band of the c³Π_u-X¹Σ_g⁺ transition is due to intensity borrowing from the strong, allowed C¹Σ_u⁺-X¹Σ_g⁺ system. Accurate values for the energies of the c³Π_u, b³Π_g, and a³Σ_u⁺ states relative to the ground state are given. The analysis of two other bands, 2-0 and 7-0, of the C¹Σ_u⁺-X¹Σ_g⁺ system whose upper levels likewise interact strongly with the c³Π_u state are also given.     

The pure rotational spectrum of ZnO in the XΣ and aΠi states

The pure rotational spectrum of ZnO has been measured in its ground X¹Σ⁺ and excited a³Π_i states using direct-absorption methods in the frequency range 239-514 GHz. This molecule was synthesized by reacting zinc vapor, generated in a Broida-type oven, with N₂O under DC discharge conditions. In the X¹Σ⁺ state, five to eight rotational transitions were recorded for each of the five isotopologues of this species (⁶⁴ZnO, ⁶⁶ZnO, ⁶⁷ZnO, ⁶⁸ZnO, and ⁷⁰ZnO) in the ground and several vibrational states (v = 1-4). Transitions for three isotopologues (⁶⁴ZnO, ⁶⁶ZnO, and ⁶⁸ZnO) were measured in the a³Π_i state for the v = 0 level, as well as from the v = 1 state of the main isotopologue. All three spin-orbit components were observed in the a³Π_i state, each exhibiting splittings due to lambda-doubling. Rotational constants were determined for the X¹Σ⁺ state of zinc oxide. The a³Π_i state data were fit with a Hund’s case (a) Hamiltonian, and rotational, spin-orbit, spin-spin, and lambda-doubling constants were established. Equilibrium parameters were also determined for both states. The equilibrium bond length determined for ZnO in the X¹Σ⁺ state is 1.7047 Å, and it increases to 1.8436 Å for the a excited state, consistent with a change from a π⁴ to a π³σ¹ configuration. The estimated vibrational constants of ω_e ∼ 738 and 562 cm⁻¹ for the ground and a state agreed well with prior theoretical and experimental investigations; however, the estimated dissociation energy of 2.02 eV for the a³Π_i state is significantly higher than previous predictions. The lambda-doubling constants suggest a low-lying ³Σ state.     

Absorption spectrum of C2 molecules near 1.06 μm

An intracavity laser spectrometer has been used to study the laser-spark absorption spectrum of C₂ radicals near 1.06 μm. The spectra recorded have been assigned, and the rotational lines of the transitions 3-0, 4-1, and 5-2 b ³Σ _g ^? -a ³Π _u and 2-1 and 1-0 A ¹Π _u -X ¹Σ _g ⁺ have been identified. The vibrational and rotational temperatures have been determined.     

State selective predissociation spectroscopy of hydrogen chloride ions (HCl+) via the A2Σ+ ← X2Π3/2 transition

The photodissociation of hydrogen chloride ions (HCl⁺) has been investigated through the A²Σ⁺ (ν′ = 6, 7 and 8) ← X ²Π_3/2 (ν″ = 0) transition. The spectra reveal that state selective photodissociation with complete resolution of the spin, orbital, and rotational angular momentum is possible in the A ²Σ⁺ (ν′ = 6) state. The analysis of these spectra yields the rotational and the spin-rotation coupling constant of the A ²Σ⁺ (ν′ = 6) state. The lifetime of HCl⁺ decreases significantly with increasing vibrational excitation in the ²Σ⁺ state. Within the experimental error limits no J dependence of the lifetime is observerd. The state selective photodissociation of the HCl⁺ ions is also shown to be a very sensitive probe for unexpected parity transitions in the 2 + 1 REMPI formation of the HCl⁺ ions in the X 2Π_3/2 (ν″ = 0) state.     

Rotational and vibrational temperatures of electronically excited BiN radicals in a chemiluminescent flame

Rotational and vibrational temperatures of electronically excited BiN radicals in a low-pressure Bi_x+N/N₂*/N₂+Ar chemiluminescent flame have been deduced from high-resolution Fourier-transform emission spectra. Bands of three electronic transitions, a³Σ⁺(a₁1)→X¹Σ⁺(X0⁺), b⁵Σ⁺(b₁0⁺)→X¹Σ⁺(X0⁺), and b⁵Σ⁺(b₁0⁺)→a ³Σ⁺(a₁1), were analysed to determine the optical temperatures in the a³Σ⁺(a₁1) and b⁵Σ⁺(b₁0⁺) states. The rotational temperatures characterising the rotational populations in the a₁1, v=0 and 1 states were determined from the a₁→X, 0-2, 0-3, 0-4, 1-1, and 1-2 bands. The b₁→X, 0-8 and 0-11 bands, and the b₁→a₁, 0-0 bands served to determine the rotational temperature of the radicals in the b₁0⁺, v=0 state. The temperatures derived from the various bands and transitions were well consistent and the mean rotational temperature was determined to be 353±18 K, which is close to the translational temperature of the gas.Vibrational temperatures of the radicals in the a₁1 and b₁0⁺ states were derived from band intensities of the a₁→X and from the b₁→X as well as b₁→a₁ systems, respectively. The Franck-Condon factors needed were calculated with RKR potentials deduced from literature values of the rotational and vibrational constants in the three states involved. The a₁1 vibrational temperature (336±21 K) was close to the rotational temperature, while the b₁0⁺ vibrational temperature (438±36 K) differed, likely due to the previously observed perturbation of the b₁0⁺ state.