Hyperfine structure in the BΠ0u state of Br2 and the influence of the perturbing 1u state

Using Doppler-free polarization spectroscopy, the hyperfine structure of the B-X system of ⁷⁹Br₂ was measured for the levels B³Π_0⁺u, v′ = 16–28, and X¹Σ_g⁺, v″ = 1, 2. Besides the nuclear electric quadrupole coupling, the magnetic spin-rotation interaction was analyzed, which varies strongly with the vibrational energy of the electronically excited state. This behavior originates from a perturbing repulsive state Ω = 1_u, the potential of which can be estimated in this way.     

Franck-Condon Factors and r-Centroids for the (B [sbnd] X) and (C [sbnd] X) Bands of the 107Ag 109Ag Molecule

Arrays of Franck-Condon factors q(v′, v″) and r-centroids r(v′, v″) were computed using Morse potentials for C¹Π [sbnd] X¹Σ⁺ _g and B O⁺ _u [sbnd] X¹Σ⁺ _g bands of the ¹⁰⁷Ag ¹⁰⁹Ag molecule.     

Intensities of the laser-induced fluorescence of 130Te2 and electronic transition strengths for the AOu+-XOg+ and BOu+-XOg+ systems

The intensities of the laser-induced fluorescence spectra of ¹³⁰Te₂, excited by Ar⁺ and He-Cd⁺ lasers, are measured for the AO_u⁺-XO_g⁺ and BO_u⁺-XO_g⁺ systems. The RKR potentials of the A, B and X states are calculated. These potentials are used for calculating Franck-Condon factors and r-centroids with due respect to rotation. The relative r-centroid dependences of the electronic transition strength were obtained first and then normalized in lifetimes.     

Examination of two new low-lying electronic states of SiS observed in chemiluminescent flame spectra

Diatomic silicon sulfide molecules have been produced in the chemiluminescent reaction of silicon atoms with OCS. Spectra of the resulting flame consist mainly of two new band systems in the region 350–400 and 385–600 nm. These systems have been assigned as b ³Π_r-X ¹Σ⁺ and a ³Σ⁺-X ¹Σ⁺ on the basis of band structure, spin-orbit splitting, molecular constants, and comparison with chemiluminescent spectra of isovalent molecules. Vibrational assignments were made with the help of the isotope effect and vibrational constants were obtained. Rotational structure was observed in some a-X bands and a partial analysis yielded an approximate rotational constant, B 0.247 ± 0.007 cm⁻¹, for the a ³Σ⁺ state. Franck-Condon factors, calculated for the a-X system, are shown to fit the general trend of the intensity distribution. Irregularities in spin-orbit splitting and in relative intensities of the spin-orbit components of the b ³Π-X ¹Σ⁺ system were observed and an attempt is made to explain them in terms of interactions with neighboring states. Addition of active nitrogen to the flame was shown to greatly increase the intensity of the b-X system relative to the a-X system. Constants (in cm⁻¹) obtained for the new state are: a³σ⁺: T_e=24 582.1 ± 1.3, ω_e=503.8±1.0, ω_ex_e=1.86±0.21b³σ⁺: T_e=27 314.5 ± 2.2, ω_e=619.4±2.0, ω_ex_e=5.75±0.52b³σ⁺: T_e=27 407.9 ± 1.1, ω_e=524.3±1.2, ω_ex_e=3.97±0.28     

High-resolution Fourier spectrometry of 15N2 infrared emission spectrum: Extensive analysis of the B3Πg-A3Σu+ system

The emission spectrum of the B³Π_g-A³Σ_u⁺ system of the ¹⁵N₂ molecule was recorded between 3500 and 12 500 cm⁻¹ with a high-resolution Fourier spectrometer. Twelve bands with 0 < v′ < 5 and 0 < v″ < 9 are analyzed. The molecular parameters of the B³Π_g and A³Σ_u⁺ states are obtained by a complete fitting procedure. Derived values of equilibrium constants are deduced; the Franck-Condon factors are calculated for the B-A system of ¹⁵N₂.     

Rotational vibrational analysis of the BΠ (0) - XΣ band system of BrCl and BrCl

24 bands of the B³Π(0⁺) ← X¹Σ⁺ system of ⁷⁹Br³⁵Cl and ⁸¹Br³⁵Cl have been photographed at high resolution. Direct least-mean square fits of the measured line frequencies were made to determine band origins and rotational constants in the ranges 1 ≤ v″ ≤ 7, 2 ≤ v′ ≤ 8. A reiterative procedure was adopted in which the higher order centrifugal distortion constants (D_v, H_v) were constrained to theoretical values calculated from RKR potential curves. The results of the analysis are used to obtain a set of Franck-Condon factors and r-centroids for the B-X system of BrCl.     

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.     

Calculation of spectroscopic constants and radiative parameters for A1Σ u+ -X1Σ g+ and B1Πu-X1Σ g+ electronic transitions of sodium dimer

Vibrational, rotational, and centrifugal spectroscopic constants and radiative parameters, i.e., the Einstein coefficients, oscillator strengths, and wave numbers for vibrational transitions in electronic systems of bands A ¹Σ _u ⁺-X ¹Σ _g ⁺ (0 ≤ v′ ≤ 25; 0 ≤ v″ ≤ 44), B ¹Π _u -X ¹Σ _g ⁺ (0 ≤ v′ ≤ 29; 0 ≤ v″ ≤ 47), and the radiative lifetimes for the vibrational levels of excited states of the sodium dimer, are calculated. The calculations are carried out based on semiempirical potential curves constructed in this study. The calculated spectroscopic constants and radiative lifetimes are compared to the experimental values.     

The electronic spectrum of bismuth monofluoride: A reinvestigation of the A0-X10 system

A reinvestigation of the A0⁺-X₁0⁺ band system, the most electronic transitions reported for bismuth monofluoride, is presented. Approximately 65 bands were photographed in emission between 4220 and 5417 Å, of which 33 were rotationally analyzed. Inconsistencies in earlier vibrational analyses were resolved. Rotational constants for 0 ≤ ν′ ≤ 12 and 0 ≤ ν″ ≤ 18 were determined from direct least-squares fitting to the measured line positions of each band. “Merging” of the overdetermined constants was performed to obtain the best single estimate of each parameter. The resulting minimum-variance linear unbiased estimates were used to calculate RKR potential curves. Franck-Condon factors and r centroids were subsequently obtained and are presented. Evidence is given for predissociation in the upper state; perturbations involving levels above the crossing point are correlated with those previously reported in the B0⁺ state. The upper limit of the ground-state dissociation energy (3.14 eV) is in accord with extrapolated values as given in earlier investigations. The nature of a postulated third interacting state is also discussed.     

Laser-induced fluorescence of Na2 at the Na(3s → 5s) two-photon transition (6022.3 Å)

Na₂ excited from the X¹Σ_g⁺ state to the A¹Σ_u⁺ state by a narrow band (3 MHz) Rhodamine-6G dye laser at 6022.3 Å, the same wavelength at which Na undergoes the 3s–5s two-photon transition, gives four fluorescence series from A¹Σ_u⁺ levels (v′ = 21, J′ = 26), (18, 33), (33, 19), and (34, 50). The last two series are much weaker in intensity, and at long wavelengths many doublets are lost in the background noise. The same (34, 50) fluorescence series was found by other workers in the lab using a Kr⁺ (5682 Å) laser as excitation source. Their analysis agrees very well with the findings in the work.     

Vibronic intensity distribution in the B0u-X0g and B1u-X1g transition of Se2

The B0_u⁺-X0_g⁺ and B1_u-X1_g transitions of ⁸⁰Se₂ and ⁷⁸Se₂ are reinvestigated. Several new bands are reported, especially for the B1_u-X1_g system, their vibrational numbering being confirmed by isotope shift studies. The Franck-Condon factors and r-centroid values are evaluated. By correlating the theoretically computed intensities with observed values, the internuclear distance dependence of the electronic transition moments of these two systems is determined for the first time.     

The E(4) Πu state in K2 and its perturbations

The E(4) ¹Π_u←X ¹Σ⁺_g band system of the K₂ molecule is investigated by the technique of Doppler-free optical–optical double resonance polarization spectroscopy. The observed vibrational levels v=0 to 9 of the E state are subject to numerous rotational perturbations by the neighboring 4 ³Π_u, 4 ¹Σ⁺_u, and 5 ³Σ⁺_u electronic states. By using deperturbation methods, the potential curves of the 4 ¹Π_u and 4 ³Π_u states are determined as well as some properties of the 4 ¹Σ⁺_u and 5 ³Σ⁺_u state potentials. The results are compared with predictions of ab initio calculations.     

Momentum transfer dependence behaviors of ionization and dissociation of oxygen

The decay pathways of the structured ionization region of oxygen at different momentum transfers,i.e.,0,0.23 a.u.(atomic unit),and 0.91 a.u.,are studied by measuring the ion and the scattered electron coincidently.It is found that the dipole-forbidden superexcited states of(2σu)-1(c4Σu-)npσu 3Σg-← X3Σg-decay into different channels according to the principal quantum number n.The broad ridge above 35 eV,which may be due to inner-valence excited states of(2σg)-1nλ or multiply excited states,is observed both at small and large momentum transfers,and its decay channel of O++ O is dominant.     

Spectroscopy of the a3Σu + state and the coupling to the X1Σg + state of K2

We report on high resolution Fourier-transform spectroscopy of fluorescence to the a³Σ_u ⁺ state induced by two-photon or two-step excitation from the X¹Σ_g ⁺ state to the 2³Π_g state in the molecule K₂. These spectroscopic data are combined with recent results of Feshbach resonances and two-color photoassociation spectra for deriving the potential curves of X¹Σ_g ⁺ and a³Σ_u ⁺ up to the asymptote. The precise relative position of the triplet levels with respect to the singlet levels was achieved by including the excitation energies from the X¹Σ_g ⁺ state to the 2³Π_g state and the frequencies of the fluorescence down to the a³Σ_u ⁺ state in the simultaneous fit of both potentials. The derived precise potential curves allow for reliable modeling of cold collisions of pairs of potassium atoms in their ²S ground state. Electronic supplementary material Supplementary Online Material     

Quantum mechanical calculation of rotational constants and Franck-Condon factors of diatomic molecules

In this paper, the question of reliability of the Morse potential as a potential curve for a diatomic molecule is investigated on the basis of calculating the rotational constant. It is shown that the Morse potential describes well potential curves of X¹Σ _q ⁺ and B¹Π_u electronic states of a Na₂ molecule. Calculations of Franck-Condon factors for X¹Σ _q ⁺ ? B¹Π_u band of a Na₂ molecule using wave functions of the Morse potential confirm the known correlation between the values of Franck-Condon factors and rotational constants of combined electronic states.     

Spectroscopic Study of the Na2 2Σg State by cw Perturbation-Facilitated Optical-Optical Double-Resonance Spectroscopy

The Na₂(3sσ_g)(4sσ_g) 2³Σ⁺_g state of Na₂ has been observed and studied by cw perturbation-facilitated optical-optical double-resonance (PFOODR) spectroscopy for the first time. A single-mode dye laser and a Ti-sapphire laser served as the pump and the probe lasers, respectively. A total of 543 PFOODR excitation signals have been assigned to the 2³Σ⁺_g ← b³Π_1u transitions. Absolute vibrational numbering was determined by counting nodes in the 2³Σ⁺_g → a³Σ⁺_u bound-free spectra. Spectroscopic constants and the corresponding RKR potential energy curve are presented in this vsork. The values of T_e, R_e, and D_e, are found to be 25 551.237(49) cm⁻¹, 3.53463(35) Å, and 6211.5(1) cm⁻¹ respectively.     

Reinvestigation of the (4, 20) band of the O2 second negative system

High resolution absorption spectra of the (4, 20) band in the second negative system (A²Π_u–X²Π_g) of O₂⁺ cation were measured and analyzed in the range of 11 900–12 300 cm^–1 via optical heterodyne velocity modulation spectroscopy. Precise molecular constants of the levels involved were obtained by a nonlinear least-squares fitting procedure combining with our previous spectra of the (4, 19) and (6, 20) bands.     

Fluorescence of Na2 and K2 excited by a gold vapor laser

The gold vapor laser has been used to irradiate the alkali dimers Li₂, Na₂, K₂, and Rb₂. Significant fluorescence was found only from Na₂ and K₂. Six fluorescent series in the A¹Σ_u⁺-X¹Σ_g⁺ system of Na₂ and three in the B¹Π_u-X¹Σ_g⁺ system of K₂ were assigned, respectively. New spectroscopic constants for the X¹Σ_g⁺ state of ³⁹K₂ are derived, and new RKR potential energy curves for the X¹Σ_g⁺ and B¹Π_u states of ³⁹K₂ are given.     

Comparison of photoelectron intensities and Franck-Condon factors in the photoionization of H2, HD and D2

The relative intensities of vibrational bands corresponding to the photoionization reactionX¹Σ_g⁺(υ″ = 0) + hv → X²Σ_g⁺(υ′ = 0, 1, 2 …) + e^? have been measured for H₂, HD and D₂, using He I radiation and a cylindrical mirror analyzer. These relative intensities differ significantly from squared overlap integrals (Franck-Condon factors) based on accurate potential curves for X¹Σ_g⁺ and X²Σ_g⁺, but are in good agreement with calculations performed by Itikawa which include the variation of transition moment with internuclear distance and the kinetic energy of the departing electron.     

High-resolution Fourier spectrometry of 14N2 infrared emission spectrum: Extensive analysis of the B3Πg-A3Σu+ system

The B³Π_g-A³Σ_u⁺ system of N₂ excited in a microwave discharge was recorded between 3 000 and 18 000 cm^?1 with a high-resolution Fourier spectrometer. There are no observed irregularities in the levels of the A³Σ_u⁺ and B³Π_g states at least for the values of v and J considered here, except the predissociation in the B³Π_g state for v = 12 and J higher than 33. This predissociation will be checked with more complete data in another article. Thirty three bands of the first positive system with 0 ≤ v′ ≤ 12 and 0 ≤ v″ ≤ 8 are analyzed. The molecular parameters of the B³Π_g and A³Σ_u⁺ are obtained by a complete fitting procedure. Derived values of equilibrium constants are deduced; RKR potential energy curves for the two states are constructed, and the Franck-Condon factors calculated for the A-B system.