Ab Initio MRD-CI Investigation of the Electronic Spectrum of Dichloromethanol Cl2CHOH

Multireference configuration interaction calculations (MRD-CI) are performed to compute excited states of dichloromethanol Cl₂CHOH, a species relevant to atmospheric chemistry. Oscillator strengths f are also calculated to predict the electronic spectrum. Four strong transitions calculated at 7.12 eV (1¹A″←X¹A′), 7.50 eV (2¹A″←X¹A′), 8.38 eV (3¹A″←X¹A′), and 8.8 eV (5¹A″←X¹A′) can serve as a guideline for experimental search. The corresponding triplet states are also given.     

Calculation of the magnetic hyperfine structure in the ground electronic state of HCCO

In this paper we analyze the spin-spin hyperfine interaction in the two components of the ground electronic state of the free π radical HCCO, A²A′[²Π] and X²A″. Electronic mean values of the Fermi contact constants of all magnetic nuclei [¹H, ¹³C₁, ¹³C₂,¹⁷O] are calculated using models that include the electron-correlation correction, primarily CCSD method in the cc-pwCVTZ basis set and B3LYP functional in the cc-pCVQZ basis set. Also, we have calculated components of the anisotropic hyperfine tensor for the ground X²A″ state. The dependence of hyperfine coupling constants (HFCCs) on the two bending coordinates is examined, and the results of HCC bending (vibrational) averaging of electronic mean values are presented for both states. It is demonstrated that electronic and subsequent vibrational averaging of the HFCCs suffices for obtaining results that are in good agreement with available experimental findings (for proton) in the X²A″ state, owing to a small geometry dependence of these quantities, and relatively distant minimum from linearity.     

Franck-Condon factors and absolute transition probabilities for the if (B3Π0+-X1Σ+) transition

Improved spectroscopic constants have been used to calculate Rydberg-Klein-Rees (RKR) potentials and Franck-Condon factors for the IF(B³Π₀₊-X¹Σ⁺) transition. The Franck-Condon factors are generally in good agreement with previously calculated values, but differ by as much as 30% for transitions from higher levels of the B-state. Several experimentally measured relative transition moment functions have been evaluated and the best scaled, so that the total transition probability calculated for each B-state vibrational level, A(v'), matched measured values. The scaled function was then used to calculate individual transition probabilities, A(v',v), for the vibronic transitions.     

New spectroscopic investigations of the fourth-positive (AΠ → XΣ) system bands in the CO molecule

The present work puts forward the results of the recordings carried out under high resolution by conventional, photographic spectroscopy and modern analysis of thirteen bands with v′ = 7-12 and v″ = 16-24 of the fourth-positive (A¹Π → X¹Σ⁺) band system. The current investigations include the region of the observed ¹³C¹⁶O molecule spectrum, much greater now than before. Especially, new transitions connected with not hitherto observed v′ = 12 vibrational level of the A¹Π state, were recorded and studied. Moreover, the region of perturbations observed in the upper state of the fourth-positive system was significantly enlarged. The observed perturbations were confronted with those predicted from theoretical calculations.     

Franck-Condon analysis of predissociations in the lower valence states of the NH radical

The origins of the predissociations observed by Smith, Brzozowski, and Erman for the A³Πand c¹Π states of NH have been investigated via a Franck-Condon analysis. It is shown that the measured variation of the predissociation probability is is proportional to the Franck-Condon densities between the bound rotational levels of the A and c states and the vibrational continuum of a ⁵Σ^- state arising from the ground state asympote. Similar calculations for the X³Σ^- ground state vibrational continuum, the only other state with a lower dissociation limit, showed that state to be ineffective in producing the observed predissociation.     

Vibrational satellites in the microwave spectrum of cyclopropylidene methanone: Extension of rigid and semirigid bender calculations to larger molecules

The microwave spectrum of cyclopropylidene methanone (CPM) at room temperature includes a large number of vibrational satellites. It has been possible to assign the spectrum of the ground state and nine additional series of satellites. Assignment to vibrational states with up to four quanta of the low-lying out-of-plane (ν₁₅) and two quanta of the in-plane (ν₂₁) bending modes was made by use of several lines of argument:

• 1.(i) relative intensities of lines of the same vibrational state for determination of the parity;
• 2.(ii) variation of A and B-C with vibrational quantum number in comparison with model calculations for in-plane and out-of-plane bending of the heavy atoms;
• 3.(iii) identification of members of the same vibrational sequence by inspection of quotients of differences of their rotational constants.

We have generalized the bender method of Bunker et al. for numerical application to larger molecules. Resulting formulae are given in the text. The rigid bender model was used to fit the changes in rotational constants of the vibrational satellites of the out-of-plane bending mode to a double minimum potential with a barrier of 38.1 ± 0.8 cm⁻¹ and minima at ±17.0 ± 0.1°. The ground state lies 5 cm⁻¹ below the barrier. The in-plane bend is almost harmonic. Its frequency of 197 cm⁻¹ was determined from an analysis of a Coriolis interaction of the v₁₅ = 3, v₂₁ = 0 state with the v₁₅ = 0, v₂₁ = 1 state. The vibrational-state dependence of the centrifugal distortion constants could be at least qualitatively reproduced in this model. The vibrational satellite shifts are equally well fitted when semirigidity is included as suggested by ab initio 4–31G MO calculations. In this case the barrier is slightly lower and the frequencies of ν₁₅ and ν₂₁ decrease by ca. 20%. On the basis of the experimental data presented here it cannot be decided whether the inclusion of semirigidity is necessary.Because the ground state out-of-plane vibrational wavefunction is practically constant over a wide range of the bending coordinate we term CPM quasisymmetric.     

High-Resolution Study of the Atilde;A′→X?A″ Transition of DO2: Analysis of the 000-000 Band

The near-infrared emission spectrum of the Atilde;²A′→X?²A″ transition of DO₂ has been studied by Fourier-transform spectrometry. The 000→000 band has been recorded at high spectral resolution. ΔK_a=±1 subbands up to K_a′=12→K_a″=11 and K_a′=9→K_a″=10, comprising lines from rotational levels up to N′=34, have been observed. With about a factor of 5-10 lower intensity, ΔK_a=0 subbands 0-0 to 6-6 were found, which are due to magnetic dipole transitions. Several local perturbations extending over 3-10 N″ values were observed. Two prominent perturbations in the F₁ levels of the òA′, 000, K_a″=11 and 12 states are attributed to ΔK_a=0, ΔJ=0, ΔN=±1 interactions with the 211 level of the X?²A″ ground state. The rotational constants for HO₂ and DO₂ have been used to deduce the molecular geometry of HO₂ at the zero point levels of the X?²A″ and òA′ states.     

High-Resolution Laser Spectroscopy of the AΠ1←XΣ System of IBr with a Titanium:Sapphire Ring Laser

The vibrotational absorption spectra of the A←X electronic transition of I^79/81Br were measured in the 11 330- to 13 220-cm⁻¹ region using a Ti:sapphire ring laser. The P-, Q-, and R-branch lines of the rotational states from J=10 to 100 belonging to the v′←v″=(3∼20)′,←(1∼6)″ bands were assigned. The P- and R-branch lines, unlike the Q-branch lines, were split into the doublet by the nuclear quadrupole coupling effect of the I atom. The quadrupole coupling constants of eQq₀ and eQq₂ in the A state were estimated to be −0.030±0.018 and −0.062±0.018 cm⁻¹, respectively, by using the first order perturbation theory. The unperturbed line positions for the rotational lines higher than J=20 were determined. The Dunham coefficients of the X state were determined by the least squares fitting method using the pseudo vibrotational transition wavenumbers obtained by calculating the combination differences between the electronic spectral lines assigned and the far infrared vibrotational lines reported by Nelander et al. (7). The spectroscopic constants of Tv′, Bv′, Dv′, and Hv′ of the A state were determined suitable for the vibrational states from v′=3 to 20 by using a least squares fitting procedure.     

High resolution emission spectroscopy of the AП-XΣ (red) system of CN

The emission spectra of the A²П-X²Σ⁺ (red) system of ¹²C¹⁴N have been reinvestigated in the 3500-22 000 cm⁻¹ region at high resolution using a Fourier transform spectrometer. In total, spectra of 63 bands involving vibrational levels up to v′ = 22 of the A²П state and v″ = 12 of the X²Σ⁺ ground state have been measured and rotationally analyzed providing an improved set of spectroscopic constants. The present measurements of the Δv = −2 sequence bands of ¹²C¹⁴N and those of ¹³C¹⁴N from Ram et al. (2010) [36] allow for a much improved identification of these two isotopologues in the near infrared spectra of carbon stars.     

A theoretical study of TeOH in its electronic ground state

The ab initio multireference single- and double-excitation configuration interaction (MRD-CI) method has been used to calculate the potential surfaces for the six lowest-lying electronic states of the TeOH molecule. The ²A″ ground state is predicted to have a bent equilibrium geometry. The first excited state, ²A′, is calculated to lie 2695 cm⁻¹ above the ground state. The MORBID program package has been used for the rotation-vibration analysis of the electronic ground state, for which the term values of the fundamental levels are calculated as 582 cm⁻¹ for the Te-O stretching mode, 959 cm⁻¹ for the bending mode, and 3655 cm⁻¹ for the O-H stretching mode.     

The BΣ state of the SO radical

Spectra of the B³Σ⁻- X³Σ⁻ transition in SO above the first dissociation limit are recorded using degenerate four wave mixing. These spectra are combined with earlier work involving laser induced fluorescence, absorption spectra and Fourier transform emission spectra, to enable a rotational analysis and deperturbation of vibrational levels of the B state up to v′ = 16. Numerous perturbations were noted within the B³Σ⁻ state, and the origin of these is discussed. In a number of cases, these perturbations can be attributed to interactions with specific other electronic states of SO, such as A³Π, C³Π, d¹Π, and A″ ³Σ⁺.     

High-resolution Fourier transform emission spectroscopy of the AΠ-XΣ system of GeSe

Natural germanium and selenium consist of, respectively, five and six stable isotopes. Several of these isotopes have considerable abundances and one should expect to observe the bands of at least six isotopic variants of germanium monoselenide (GeSe). In this paper, for the first time, the results of the high-resolution electronic spectrum of the main transition A¹Π-X¹Σ⁺ of the specific isotopomer ⁷⁴Ge⁸⁰Se, excited in a microwave discharge and recorded in the 33 500-26 000 cm⁻¹ region using a Fourier transform spectrometer, is discussed. From the rotational analysis of 25 bands involving v″ = 0-12 and v′ = 0-7, accurate vibrational and rotational constants of the A¹Π state are determined. The present study has revealed perturbations in the v′ = 6 and 7 levels of the A¹Π state.     

Fourier transform spectroscopy of chemiluminescence from the AΠ-XΣ system of SrO

The A^′1Π-X¹Σ⁺ near infrared system of strontium oxide (SrO) was observed at high spectral resolution by measuring the chemiluminescence from a Broida flow reactor using a Fourier transform spectrometer. In total, 32 bands from , , were measured within the spectral region at a resolution of . Vibrational levels of the upper state were observed up to v_A^′=4, and more than 5600 rotational lines were assigned. Incorporating previously published high resolution data for the A¹Σ⁺-X¹Σ⁺ system, a global fit to both data sets yields improved Dunham constants for the ground state and for the lower vibrational levels (v_A^′=0, 1, and 2) of the A^′1Π state. Because perturbations arising from interactions with the b³Σ⁺ and A¹Σ⁺ states affect the higher vibrational levels of the A^′1Π state more strongly, levels v_A^′=3 and 4 were represented by effective band constants in the fits. RKR potentials for the X¹Σ⁺,A^′1Π, and b³Σ⁺ states have been generated utilizing all the available data, Franck-Condon factors have been calculated for the A^′1Π-X¹Σ⁺ system, and A^′1Π∼b³Σ⁺ and A^′1Π∼A¹Σ⁺ perturbations are discussed.     

The laser-induced fluorescence study of AΣ-XΠi band system of CuS

The laser-induced fluorescence excitation spectra of jet-cooled CuS molecules have been recorded in the energy range of 17 200-19 500 cm⁻¹. Fourteen observed vibronic bands have been assigned as three transition progressions: A²Σ⁻ (v′ = 0-4)-X²Π_3/2 (v″ = 0), A²Σ⁻ (v′ = 0-4)-X²Π_3/2 (v″ = 1), and A²Σ⁻ (v′ = 0-3)-X²Π_1/2 (v″ = 0). Spectroscopic constants of both the X²Π ground state and the A²Σ⁻ excited state of ⁶³CuS and ⁶⁵CuS were determined by analyzing their rotationally resolved spectra. Furthermore, the lifetimes of most observed bands were measured for the first time.     

Diode laser jet spectra and analysis of the ν14 fundamental of 1,1,1,2-tetrafluoroethane (HFC-134a)

High resolution infrared spectra have been measured for mixtures of 1,1,1,2-tetrafluoroethane in Ne, expanded in a supersonic planar jet. The ν₁₄ fundamental is an essentially unperturbed C-type band, exhibiting many ΔK_c=±2 transitions. Accurate excited state rotational and distortion constants have been determined from an analysis of about 1250 transitions, by using Watson’s Hamiltonian in the S-reduction. A local perturbation has been observed with a crossing at K^′_a=11 for J^′ values between 17 and 18, and could be accounted for by a x-Coriolis interaction with a perturbing vibrational level of A^′ symmetry at about 1205.53(1) cm⁻¹. Due to the very efficient cooling in the jet, the rotational temperature resulted to be about 20 K, and no evidence of hot-band absorption was found.     

Radiative rates and electron impact excitation rate coefficients for H-like Fe XXVI

In this paper we report on calculations on energy levels, radiative rates, collision strengths, and effective collision strengths for transitions among the lowest 36 levels of the n≤6 configurations of H-like Fe XXVI. Flexible atomic code (FAC) is adopted for the calculation. Energy levels and radiative rates are calculated within relativistic configuration-interaction method. Direct excitation collision strength is calculated using relativistic distorted-wave approximation. Resonance contributions through the relevant He-like doubly excited n^′l^′n^″l^″ configurations with n^′≤7 and n^″≤75 are explicitly taken into account using the isolated process and isolated resonances approximation. We present the radiative rates, oscillator strengths, and line strengths for all electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), and magnetic quadrupole (M2) transitions among the 36 levels. Furthermore, collision strengths and effective collision strengths are reported for all the 630 transitions among the above 36 levels over a wide energy (temperature) range up to 25 keV . Extensive comparisons are made with earlier available results and the accuracy of the data is assessed.     

The Rotational Spectrum of ClClO2 in Its v4=1 and v6=1 Vibrationally Excited States: An Example of Strong Coriolis Interaction

The two lowest vibrational states of ³⁵Cl³⁵ClO₂, v₄=1 (A′) and v₆=1 (A″), were investigated between 223 and 500 GHz. More than 250 rotational transitions were recorded with J and K_a up to 71 and 34, respectively. The spectra are heavily perturbed by strong c-type and weaker a-type Coriolis interactions. Near degeneracies of rotational levels of the two vibrational states having ΔJ=0, ΔK_a=5 to 1, and ΔK_a+ΔK_c= odd cause moderate to severe perturbations in the rotational structure, preventing the states from being fit as isolated ones. Distortions in the hyperfine structure facilitated the assignment of rotational quantum numbers. Several resonantly interacting levels with ΔK_a=5 to 2 were accessed, and a number of transitions between the states were observed. While resonant Coriolis interaction with ΔK_a=1 occurs only at K_a>40, the effects of this interaction are so severe that nonresonant interaction considerably perturbs the highest K_aQ-branches observed. The observed transitions could be fit to within experimental uncertainties employing the first-order Coriolis coupling constants fixed to those from the harmonic force field, sextic distortion constants fixed to those of the ground state, and some higher order Coriolis terms. The energy difference calculated from the fit agrees well with that obtained from the matrix-isolation infrared spectrum. Quadrupole coupling constants were determined for both Cl nuclei and both vibrational states.     

The electronic emission spectrum of SiB

The gas phase spectrum of the silicon boride radical has been observed for the first time. Two electronic transitions were observed in emission from a corona excited supersonic expansion source. The D⁴Σ⁻-X⁴Σ⁻ system consists of emission from v′ = 0 to v″ = 0-3, while the A⁴Π-X⁴Σ⁻ system consists of numerous bands with v′ = 0-5 and v″ = 0-11, although only the strong 0-0 and 0-1 bands have been analyzed so far.     

The rotational spectrum of acrylonitrile in excited states of the two low-frequency CCN bending vibrational modes

The strongest vibrational satellites in the rotational spectrum of acrylonitrile have been assigned and frequencies of μ_a- and μ_b-type transitions in the frequency range 27–184 GHz are reported for the first two excited states in the lowest frequency in-plane CCN bending vibrational mode and the first excited state in the out-of-plane CCN bending mode. The values of the rotational constants, the quartic and sextic centrifugal distortion constants, and one octic centrifugal distortion constant are determined for each of these states. Less extensive results are also presented for the third quantum of the in-plane bend. The data set for the ground state has been extended by a number of new measurements and the improved ground state constants are used in a discussion of changes in rotational and centrifugal distortion constants with vibrational state where all constants associated with P_zⁿ and P²P_z⁽ⁿ⁻²⁾ terms in the Hamiltonian are found to reflect the common origin of the two CCN bends.     

First- and second-order Coriolis interactions in symmetric top molecules: Application to the microwave spectrum of cyclopentadienyl thallium

Matrix elements are derived for both first- and second-order Coriolis interactions between A₁ and E₁ vibrational modes in symmetric tops, with particular reference to sign. The results are applied to the observed microwave transitions J → J + 1 for A₁ and E₁ states of the C_5ν molecule cyclopentadienyl thallium in various excited vibrational states. The microwave transitions in the excited A₁ states v₄ = 1, 2, 3, the excited E′ state v′₀ = 1 and the combination state v₄ = 1, v′₀ = 1 have yielded constants which are anomalous in several respects (1). Coriolis interactions between the ν₄ and ν₁₀ vibrations are shown to account for the observed anomalies.