MARVEL analysis of high-resolution rovibrational spectra of 16O12C18O.

Empirical rovibrational energy levels are presented for the third most abundant, asymmetric carbon dioxide isotopologue, 16O12C18O, based on a compiled dataset of experimental rovibrational transitions collected from the literature. The 52 literature sources utilized provide 19,438 measured lines with unique assignments in the wavenumber range of 2-12,676 cm-1. The MARVEL (Measured Active Rotational-Vibrational Energy Levels) protocol, which is built upon the theory of spectroscopic networks, validates the great majority of these transitions and outputs 8786 empirical rovibrational energy levels with an uncertainty estimation based on the experimental uncertainties of the transitions. Issues found in the literature data, such as misassignment of quantum numbers, typographical errors, and misidentifications, are fixed before including them in the final MARVEL dataset and analysis. Comparison of the empirical energy-level data of this study with those in the line lists CDSD-2019 and Ames-2021 shows good overall agreement, significantly better for CDSD-2019; some issues raised by these comparisons are discussed.

Predissociation dynamics of the hydroxyl radical (OH) based on a five-state spectroscopic model.

Multi-reference configuration interaction potential energy curves (PECs) and spin-orbit couplings for the X 2Π, A 2Σ+, 1 2Σ-, 1 4Σ-, and 1 4Π states of OH are computed and refined against empirical energy levels and transitions to produce a spectroscopic model. Predissociation lifetimes are determined by discretizing continuum states in the variational method nuclear motion calculation by restricting the calculation to a finite range of internuclear separations. Varying this range gives a series of avoided crossings between quasi-bound states associated with the A 2Σ+ and continuum states, from which predissociation lifetimes are extracted. 424 quasi-bound A 2Σ+ state rovibronic energy levels are analyzed, and 374 predissociation lifetimes are produced, offering good coverage of the predissociation region. Agreement with measured lifetimes is satisfactory, and a majority of computed results were within experimental uncertainty. A previously unreported A 2Σ+ state predissociation channel that goes via X 2Π is identified in the calculations. A Python package, binSLT, produced to calculate predissociation lifetimes, associated line broadening parameters, and lifetime uncertainties is made available. The PECs and other curves from this work will be used to produce a rovibronic ExoMol line list and temperature-dependent photodissociation cross sections for the hydroxyl radical.

Dissociation of Hydrofluorocarbon Molecules after Electron Impact in Plasma.

The process of dissociation for two hydrofluorocarbon molecules in low triplet states excited by electron impact in plasma is investigated by ab initio molecular dynamics (AIMD). The interest in the dissociation of hydrofluorocarbons in plasma is motivated by their role in plasma etching in microelectronic technologies. Dissociation of triplet states is very fast, and the reaction products can be predicted. In this work, it was found that higher triplet states relax into the lowest triplet state within a few femtoseconds due to nonadiabatic dynamics, such that the simplest ab initio MD on the lowest triplet state seems to give a reasonable estimate of the reaction channels branching ratios. We provide evidence of the existence of simple rules for the dissociation of hydrofluorocarbon molecules in triplet states. For molecules with a double bond, the bonds adjacent to the double bond dissociate faster than the other bonds.

The infrared absorption spectrum of radioactive water isotopologue H215O.

A room temperature line list for the H215O radioactive isotopologue of the water molecule is computed using the variational nuclear-motion DVR3D program suite and an empirical high-precision potential energy function. The line list consists of rotation-vibrational energies and Einstein-A coefficients, covering a wide spectral range from 0 to 25000 cm-1 and the total angular momenta J up to 30. Estimates of air-broadening coefficients are provided. Experimentally derived energies of H216O, H217O and H218O from the literature are used to provide improved energies for important states with uncertainty estimates for the H215O. A number of the wmost promising spectroscopic ranges for the detection of H215O are proposed. The calculated absorption spectrum should be useful for the study gaseous radioactive water at IR region, determining concentration, etc.

Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules.

The (time-independent) Schrödinger equation for atomistic systems is solved by using the adiabatic potential energy curves (PECs) and the associated adiabatic approximation. In cases where interactions between electronic states become important, the associated nonadiabatic effects are taken into account via derivative couplings (DDRs), also known as nonadiabatic couplings (NACs). For diatomic molecules, the corresponding PECs in the adiabatic representation are characterized by avoided crossings. The alternative to the adiabatic approach is the diabatic representation obtained via a unitary transformation of the adiabatic states by minimizing the DDRs. For diatomics, the diabatic representation has zero DDR and nondiagonal diabatic couplings ensue. The two representations are fully equivalent and so should be the rovibronic energies and wave functions, which result from the solution of the corresponding Schrödinger equations. We demonstrate (for the first time) the numerical equivalence between the adiabatic and diabatic rovibronic calculations of diatomic molecules using the ab initio curves of yttrium oxide (YO) and carbon monohydride (CH) as examples of two-state systems, where YO is characterized by a strong NAC, while CH has a strong diabatic coupling. Rovibronic energies and wave functions are computed using a new diabatic module implemented in the variational rovibronic code Duo. We show that it is important to include both the diagonal Born-Oppenheimer correction and nondiagonal DDRs. We also show that the convergence of the vibronic energy calculations can strongly depend on the representation of nuclear motion used and that no one representation is best in all cases.

MARVEL analysis of high-resolution rovibrational spectra of 13 C 16 O 2 .

A set of empirical rovibrational energy levels, obtained through the MARVEL (measured active rotational-vibrational energy levels) procedure, is presented for the 13 C 16 O 2 isotopologue of carbon dioxide. This procedure begins with the collection and analysis of experimental rovibrational transitions from the literature, allowing for a comprehensive review of the literature on the high-resolution spectroscopy of 13 C 16 O 2 , which is also presented. A total of 60 sources out of more than 750 checked provided 14,101 uniquely measured and assigned rovibrational transitions in the wavenumber range of 579-13,735 cm - 1 . This is followed by a weighted least-squares refinement yielding the energy levels of the states involved in the measured transitions. Altogether 6318 empirical rovibrational energies have been determined for 13 C 16 O 2 . Finally, estimates have been given for the uncertainties of the empirical energies, based on the experimental uncertainties of the transitions. The detailed analysis of the lines and the spectroscopic network built from them, as well as the uncertainty estimates, all serve to pinpoint possible errors in the experimental data, such as typos, misassignment of quantum numbers, and misidentifications. Errors found in the literature data were corrected before including them in the final MARVEL dataset and analysis.

Measurement and calculation of CO (7-0) overtone line intensities.

Intensities of 14 lines in the sixth overtone (7-0) band of carbon monoxide (12C16O) are measured in the visible range between 14 300 and 14 500 cm-1 using a frequency-stabilized cavity ring-down spectrometer. This is the first observation of such a high and weak overtone spectrum of the CO molecule. A theoretical model is constructed and tested based on the use of a high accuracy ab initio dipole moment curve and a semi-empirical potential energy curve. Accurate studies of high overtone transitions provide a challenge to both experiment and theory as the lines are very weak: below 2 × 10-29 cm molecule-1 at 296 K. Agreement between theory and experiment within the experimental uncertainty of a few percent is obtained. However, this agreement is only achieved after issues with the stability of the Davidson correction to the multi-reference configuration interaction calculations are addressed.

Elastic and inelastic low-energy electron scattering from pyridine.

A comprehensive investigation of elastic and inelastic electron scattering from molecular pyridine is reported using the ab initio R-matrix method with the static exchange plus polarization and close-coupling approximations for incident energies up to 10 eV. The two well-known low-lying 1 2B1 and 1 2A2 shape resonances as well as a 2 2B1 mixed-character resonance compare well with the theoretical and experimental results. We also detect five core-excited resonances (1 2A1, 1 2B2, 3 2B1, 2 2A2, and 4 2B1), which lie above the first electronic excitation threshold. The total elastic cross sections and momentum transfer cross sections agree reasonably with previous reference data. Comparisons of the differential elastic cross sections of pyridine with those measured for benzene, pyrazine, and pyrimidine show remarkable agreement at scattering angles above 40° but behave differently for forward scattering below 40° below 6 eV, due to the dominant effect of the permanent dipole moment on the differential cross section in the low energy region with narrow scattering angles. Inelastic electronic excitation cross sections are presented, showing the influence of core-excited resonances below the ionization threshold for the first time.

A variational model for the hyperfine resolved spectrum of VO in its ground electronic state.

A variational model for the infra-red spectrum of vanadium monoxide (VO) is presented, which aims to accurately predict the hyperfine structure within the VO XΣ-4 electronic ground state. To give the correct electron spin splitting of the XΣ-4 state, electron spin dipolar interaction within the ground state and the spin-orbit coupling between XΣ-4 and two excited states, AΠ4 and 1Σ+2, are calculated ab initio alongside hyperfine interaction terms. Four hyperfine coupling terms are explicitly considered: Fermi-contact interaction, electron spin-nuclear spin dipolar interaction, nuclear spin-rotation interaction, and nuclear electric quadrupole interaction. These terms are included as part of a full variational solution of the nuclear-motion Schrödinger equation performed using program Duo, which is used to generate both hyperfine-resolved energy levels and spectra. To improve the accuracy of the model, ab initio curves are subject to small shifts. The energy levels generated by this model show good agreement with the recently derived empirical term values. This and other comparisons validate both our model and the recently developed hyperfine modules in Duo.

Analysis of measured high-resolution doublet rovibronic spectra and related line lists of 12CH and 16OH.

Detailed understanding of the energy-level structure of the quantum states as well as of the rovibronic spectra of the ethylidyne (CH) and the hydroxyl (OH) radicals is mandatory for a multitude of modelling efforts within multiple chemical, combustion, astrophysical, and atmospheric environments. Accurate empirical rovibronic energy levels, with associated uncertainties, are reported for the low-lying doublet electronic states of 12CH and 16OH, using the Measured Active Rotational-Vibrational Energy Levels (MARVEL) algorithm. For 12CH, a total of 1521 empirical energy levels are determined in the primary spectroscopic network (SN) of the radical, corresponding to the following seven electronic states: X 2Π, A 2Δ, B 2Σ-, C2 Σ+, D 2Π, E 2Σ+, and F 2Σ+. The energy levels are derived from 6348 experimentally measured and validated transitions, collected from 29 sources. For 16OH, the lowest four doublet electronic states, X 2Π, A 2Σ+, B 2Σ+, and C 2Σ+, are considered, and a careful analysis and validation of 15 938 rovibronic transitions, collected from 45 sources, results in 1624 empirical rovibronic energy levels. The large set of spectroscopic data presented should facilitate the refinement of line lists for the 12CH and 16OH radicals. For both molecules hyperfine-resolved experimental transitions have also been considered, forming SNs independent from the primary SNs.

Subpromille Measurements and Calculations of CO (3-0) Overtone Line Intensities.

Intensities of lines in the near-infrared second overtone band (3-0) of ^{12}C^{16}O are measured and calculated to an unprecedented degree of precision and accuracy. Agreement between theory and experiment to better than 1‰ is demonstrated by results from two laboratories involving two independent absorption- and dispersion-based cavity-enhanced techniques. Similarly, independent Fourier transform spectroscopy measurements of stronger lines in this band yield mutual agreement and consistency with theory at the 1‰ level. This set of highly accurate intensities can provide an intrinsic reference for reducing biases in future measurements of spectroscopic peak areas.

Highly accurate HF dimer ab initio potential energy surface.

A highly accurate, (HF)2 potential energy surface (PES) is constructed based on ab initio calculations performed at the coupled-cluster single double triple level of theory with an aug-cc-pVQZ-F12 basis set at about 152 000 points. A higher correlation correction is computed at coupled-cluster single double triple quadruple level for 2000 points and is considered alongside other more minor corrections due to relativity, core-valence correlation, and Born-Oppenheimer failure. The analytical surface constructed uses 500 constants to reproduce the ab initio points with a standard deviation of 0.3 cm-1. Vibration-rotation-inversion energy levels of the HF dimer are computed for this PES by variational solution of the nuclear-motion Schrödinger equation using the program WAVR4. Calculations over an extended range of rotationally excited states show very good agreement with the experimental data. In particular, the known empirical rotational constants B for the ground vibrational states are predicted to better than about 2 MHz. B constants for excited vibrational states are reproduced several times more accurately than by previous calculations. This level of accuracy is shown to extend to higher excited inter-molecular vibrational states v and higher excited rotational quantum numbers (J, Ka).

A Method for the Variational Calculation of Hyperfine-Resolved Rovibronic Spectra of Diatomic Molecules.

An algorithm for the calculation of hyperfine structure and spectra of diatomic molecules based on the variational nuclear motion is presented. The hyperfine coupling terms considered are Fermi-contact, nuclear spin-electron spin dipole-dipole, nuclear spin-orbit, nuclear spin-rotation, and nuclear electric quadrupole interactions. Initial hyperfine-unresolved wave functions are obtained for a given set of potential energy curves and associated couplings by a variation solution of the nuclear-motion Schrödinger equation. Fully hyperfine-resolved parity-conserved rovibronic Hamiltonian matrices for a given final angular momentum, F, are constructed and then diagonalized to give hyperfine-resolved energies and wave functions. Electric transition dipole moment curves can then be used to generate a hyperfine-resolved line list by applying rigorous selection rules. The algorithm is implemented in Duo, which is a general program for calculating spectra of diatomic molecules. This approach is tested for NO and MgH, and the results are compared to experiment and shown to be consistent with those given by the well-used effective Hamiltonian code PGOPHER.

Rovibronic spectroscopy of PN from first principles.

We report an ab initio study on the rovibronic spectroscopy of the closed-shell diatomic molecule phosphorous mononitride, PN. The study considers the nine lowest electronic states, X 1Σ+, A 1Π, C 1Σ-, D 1Δ, E 1Σ-, a 3Σ+, b 3Π, d 3Δ and e 3Σ- using high level electronic structure theory and accurate nuclear motion calculations. The ab initio data cover 9 potential energy, 14 spin-orbit coupling, 7 electronic angular momentum coupling, 9 electric dipole moment and 8 transition dipole moment curves. The Duo nuclear motion program is used to solve the coupled nuclear motion Schrödinger equations for these nine electronic states and to simulate rovibronic absorption spectra of 31P14N for different temperatures, which are compared to available spectroscopic studies. Lifetimes for all states are calculated and compared to previous results from the literature. The calculated lifetime of the A1Π state shows good agreement with an experimental value from the literature, which is an important quality indicator for the ab initio A-X transition dipole moment.

Electric quadrupole transitions in carbon dioxide.

Recent advances in high sensitivity spectroscopy have made it possible, in combination with accurate theoretical predictions, to observe, for the first time, very weak electric quadrupole transitions in a polar polyatomic molecule of water. Here, we present accurate theoretical predictions of the complete quadrupole rovibrational spectrum of a non-polar molecule CO2, important in atmospheric and astrophysical applications. Our predictions are validated by recent cavity enhanced absorption spectroscopy measurements and are used to assign few weak features in the recent ExoMars Atmospheric Chemistry Suite mid-infrared spectroscopic observations of the Martian atmosphere. Predicted quadrupole transitions appear in some of the mid-infrared CO2 and water vapor transparency regions, making them important for detection and characterization of the minor absorbers in water- and CO2-rich environments, such as those present in the atmospheres of Earth, Venus, and Mars.

Theoretical rovibronic spectroscopy of the calcium monohydroxide radical (CaOH).

The rovibronic (rotation-vibration-electronic) spectrum of the calcium monohydroxide radical (CaOH) is of interest to studies of exoplanet atmospheres and ultracold molecules. Here, we theoretically investigate the Ã2Π-X̃2Σ+ band system of CaOH using high-level ab initio theory and variational nuclear motion calculations. New potential energy surfaces (PESs) are constructed for the X̃2Σ+ and Ã2Π electronic states along with Ã-X̃ transition dipole moment surfaces (DMSs). For the ground X̃2Σ+ state, a published high-level ab initio PES is empirically refined to all available experimental rovibrational energy levels up to J = 15.5, reproducing the observed term values with a root-mean-square error of 0.06 cm-1. Large-scale multireference configuration interaction calculations using quintuple-zeta quality basis sets are employed to generate the Ã2Π state PESs and Ã-X̃ DMSs. Variational calculations consider both Renner-Teller and spin-orbit coupling effects, which are essential for a correct description of the spectrum of CaOH. Computed rovibronic energy levels of the Ã2Π state, line list calculations up to J = 125.5, and an analysis of Renner-Teller splittings in the ν2 bending mode of CaOH are discussed.

A method for calculating temperature-dependent photodissociation cross sections and rates.

The destruction of molecules by photodissociation plays a major role in many radiation-rich environments, including the evolution of the atmospheres of exoplanets, which often exist close to UV-rich stars. Most current photodissociation calculations and databases assume T = 0 K, which is inadequate for hot exoplanets and stars. A method is developed for computing photodissociation spectra of diatomic molecules as a function of temperature exploiting bound state variational nuclear motion program Duo and post-processing program ExoCross. Discrete transition intensities are spread out to represent a continuous photodissociation spectrum either by Gaussian smoothing or by averaging calculations over a range of different grid sizes. Our approach is tested on four different chemical species (HCl, HF, NaCl and BeH+), showing its ability to reproduce photodissociation cross sections and rates computed with other approaches and experiment. The temperature dependence of photodissociation cross sections and rates is studies showing strong temperature variation of the photodissociation cross sections.

Ionisation of PF3: absolute partial electron ionisation cross sections and the formation and reactivity of dication states.

Absolute partial electron ionisation cross sections, and precursor-specific partial electron ionisation cross sections, for the formation of cations from phosphorus trifluoride (PF3) are reported over the electron energy range 50-200 eV. The absolute values are determined by the measurement of cross sections relative to the formation of PF3+ using 2D ion-ion coincidence time-of-flight mass spectrometry and subsequent scaling using binary encounter-Bethe calculations of the total ionisation cross section. This new dataset significantly augments the partial ionisation cross sections for electron ionization of PF3 found in literature, addressing previous discrepancies in the branching ratios of product ions, and provides the first values for the precursor-specific cross sections. Comparisons to calculated cross sections from the literature are encouraging, although there are discrepancies for individual ions. The coincidence experiments indicate that double and triple ionisation generate approximately 20% of the cationic ionisation products at 200 eV electron energy. One dissociative dication state, dissociating to PF2+ + F+, is clearly identified as the lowest triplet state of PF32+ and five different dications (PF32+, PF22+, PF2+, P2+ and F2+) are detected in the mass spectra. The dication energetics revealed by the experiments are supported by a computational investigation of the dication's electronic structure. The cross sections reported will allow more accurate modelling of the role of the ionization of PF3 in energetic environments. A first investigation of the bimolecular reactivity of metastable states of PF32+ is also reported. In collisions with Ar, O2 and CO dissociative single electron transfer dominates the product ion yield, whereas collision-induced dissociation of the dication is important following collisions with Ne. Consideration of the energetics of these processes indicates that the reactant dication beam contains ions in both the ground singlet state and the first excited triplet state. The deduction regarding the longevity of the triplet state is supported by metastable signals in the coincidence spectra. Weak signals corresponding to the formation of ArF+ are detected following PF32+ collisions with Ar, and experimental and computational considerations indicate this new chemical bond is formed via a collision complex.

The efficient calculation of electron impact ionization cross sections with effective core potentials.

A black box Binary Encounter Bethe (BEB) with an effective core potential (ECP) procedure is implemented, which facilitates the efficient calculation of electron impact ionization cross sections for molecules that include heavy atoms. This is available in the Quantemol electron collisions software, a user friendly graphical user interface to the UKRMol+ codes. Tests were performed for the following series of molecules: CF4, CCl4, CBr4, CI4, and CAt4; CH4, SiH4, GeH4, and SnH4; PH3, PF3, and PCl3; SiCl4 and BCl3; and CH3Br and CF3I. Use of an ECP generally raises the predicted ionization cross section at lower energies leading to improved agreement with experiment compared to all electron calculations for BEB cross sections. Scaling BEB cross sections by the polarizability of the target molecule is shown to give somewhat erratic results, which do not always provide closer agreement with the measured cross sections.

A spectroscopic model for the low-lying electronic states of NO.

The rovibronic structure of A2Σ+, B2Π, and C2Π states of nitric oxide (NO) is studied with the aim of producing comprehensive line lists for its near ultraviolet spectrum. Empirical energy levels for the three electronic states are determined using a combination of the empirical measured active rotation-vibration energy level (MARVEL) procedure and ab initio calculations, and the available experimental data are critically evaluated. Ab initio methods that deal simultaneously with the Rydberg-like A2Σ+ and C2Π and the valence B2Π state are tested. Methods of modeling the sharp avoided crossing between the B2Π and C2Π states are tested. A rovibronic Hamiltonian matrix is constructed using the variational nuclear motion program Duo whose eigenvalues are fitted to the MARVEL. The matrix also includes coupling terms obtained from the refinement of the ab initio potential energy and spin-orbit coupling curves. Calculated and observed energy levels agree well with each other, validating the applicability of our method and providing a useful model for this open shell system.