Potential energy surface, dipole moment surface and the intensity calculations for the 10 µm, 5 µm and 3 µm bands of ozone

Monitoring ozone concentrations in the Earth's atmosphere using spectroscopic methods is a major activity which undertaken both from the ground and from space. However there are long-running issues of consistency between measurements made at infrared (IR) and ultraviolet (UV) wavelengths. In addition, key O 3 IR bands at 10 µm, 5 µm and 3 µm also yield results which differ by a few percent when used for retrievals. These problems stem from the underlying laboratory measurements of the line intensities. Here we use quantum chemical techniques, first principles electronic structure and variational nuclear-motion calculations, to address this problem. A new high-accuracy ab initio dipole moment surface (DMS) is computed. Several spectroscopically-determined potential energy surfaces (PESs) are constructed by fitting to empirical energy levels in the region below 7000 cm−1 starting from an ab initio PES. Nuclear motion calculations using these new surfaces allow the unambiguous determination of the intensities of 10 µm band transitions, and the computation of the intensities of 10 µm and 5 µm bands within their experimental error. A decrease in intensities within the 3 µm is predicted which appears consistent with atmospheric retrievals. The PES and DMS form a suitable starting point both for the computation of comprehensive ozone line lists and for future calculations of electronic transition intensities

Calculated line lists for H216O and H218O with extensive comparisons to theoretical and experimental sources including the HITRAN2016 database

New line lists are presented for the two most abundant water isotopologues; H216O and H218O. The H216O line list extends to 25710 cm with intensity stabilities provided via ratios of calculated intensities obtained from two different semi-empirical potential energy surfaces. The line list for H218O extends to 20000 cm. The minimum intensity considered for all is cm molecule at 296 K, assuming 100% abundance for each isotopologue. Fluctuation of calculated intensities caused by changes in the underlying potential energy are found to be significant, particularly for weak transitions. Direct comparisons are made against eighteen different sources of line intensities, both experimental and theoretical, many of which are used within the HITRAN2016 database. With some exceptions, there is excellent agreement between our line lists and the experimental intensities in HITRAN2016. In the infrared region, many H216O bands which exhibit intensity differences of 5–10% between to the most recent ’POKAZATEL’ line list (Polyansky et al., [Mon. Not. Roy. Astron. Soc. 480, 2597 (2018)] and observation, are now generally predicted to within 1%. For H218O, there are systematic differences in the strongest intensities calculated in this work versus those obtained from semi-empirical calculations. In the visible, computed cross sections show smaller residuals between our work and both HITRAN2016 and HITEMP2010 than POKAZATEL. While our line list accurately reproduces HITEMP2010 cross sections in the observed region, residuals produced from this comparison do however highlight the need to update line positions in the visible spectrum of HITEMP2010. These line lists will be used to update many transition intensities and line positions in the HITRAN2016 database

ExoMol molecular line lists XIX: high-accuracy computed hot line lists for H218O and H217O

Hot line lists for two isotopologues of water, H218O and H217O, are presented. The calculations employ newly constructed potential energy surfaces (PES), which take advantage of a novel method for using the large set of experimental energy levels for H216O to give high-quality predictions for H218O and H217O. This procedure greatly extends the energy range for which a PES can be accurately determined, allowing an accurate prediction of higher lying energy levels than are currently known from direct laboratory measurements. This PES is combined with a high-accuracy, ab initio dipole moment surface of water in the computation of all energy levels, transition frequencies and associated Einstein A coefficients for states with rotational excitation up to J = 50 and energies up to 30 000 cm−1. The resulting HotWat78 line lists complement the well-used BT2 H216O line list. Full line lists are made available online as Supporting Information and at www.exomol.com

The W2020 Database of Validated Rovibrational Experimental Transitions and Empirical Energy Levels of Water Isotopologues. II. (H2O)-O-17 and (H2O)-O-18 with an Update to (H2O)-O-16

The W2020 database of validated experimental transitions and accurate empirical energy levels of water isotopologues, introduced in the work of Furtenbacher et al. [J. Phys. Chem.Ref.Data 49, 033101 (2020)], is updated forH2 16Oand newly populated with data forH2 17OandH2 18O. TheH2 17O/ H2 18O spectroscopic data utilized in this study are collected from 65/87 sources, with the sources arranged into 76/99 segments, and the data in these segments yield 27 045/66 166 (mostly measured) rovibrational transitions and 5278/6865 empirical energy levels with appropriate uncertainties. Treatment and validation of the collated transitions of H2 16O, H2 17O, and H2 18O utilized the latest, XML-based version of the MARVEL (Measured Active Rotational-Vibrational Energy Levels) protocol and code, called xMARVEL. The empirical rovibrational energy levels of H2 17O and H2 18O form a complete set through 3204 cm−1 and 4031 cm−1, respectively. Vibrational band origins are reported for 37 and 52 states of H2 17O andH2 18O, respectively. The spectroscopic data of this study extend and improve the data collated by an InternationalUnion of Pure andApplied ChemistryTask Group in 2010 [J. Tennyson et al., J. Quant. Spectrosc. Radiat. Transfer 110, 2160 (2010)] as well as those reported in the HITRAN2016 information system. Following aminor but significant update to theW2020-H2 16Odataset, the joint analysis of the rovibrational levels for the seriesH2 16O,H2 17O, andH2 18Ofacilitated development of a consistent set of labels among these threewater isotopologues and the provision of accurate predictions of yet to be observed energy levels for the minor isotopologues using the combination of xMARVEL results and accurate variational nuclear-motion calculations. To this end, 9925/8409pseudo-experimental levels have been derived forH2 17O/H2 18O, significantly improving the coverage of accurate lines for these twominor water isotopologues up to the visible region. The W2020 database now contains almost all of the transitions, apart from those of HD16O, required for a successful spectroscopic modeling of atmospheric water vapor

ExoMol molecular line lists – XX. A comprehensive line list for H3+

H3+ is a ubiquitous and important astronomical species whose spectrum has been observed in the interstellar medium, planets and tentatively in the remnants of supernova SN1897a. Its role as a cooler is important for gas giant planets and exoplanets, and possibly the early Universe. All this makes the spectral properties, cooling function and partition function of H3+ key parameters for astronomical models and analysis. A new high-accuracy, very extensive line list for H3+ called MiZATeP was computed as part of the ExoMol project alongside a temperature-dependent cooling function and partition function as well as lifetimes for excited states. These data are made available in electronic form as supplementary data to this article and at www.exomol.com

Room temperature line lists for deuterated water

Line lists are presented for six deuterated isotopologues of water vapor namely HD16O, HD17O, HD18O, D16 2 O, D17 2 O and D18 2 O. These line lists are prepared using empirically-determined energy levels, where available, to provide transition frequencies and high-quality ab initio dipole moment surfaces to provide transition intensities. The reliability of the predicted intensities is tested by computing multiple line lists and analyzing the stability of the results. The resulting intensities are expected to be accurate to a few percent for well-behaved, stable transitions. Complete T = 296 K line lists are provided for each species

Analysis of the red and green optical absorption spectrum of gas phase ammonia

Room temperature NH 3 absorption spectra recorded at the Kitt Peak National Solar Observatory in 1980 are analyzed. The spectra cover two regions in the visible: 15,200 – 15,700 cm−1 and 17,950 – 18,250 cm−1. These high overtone rotation-vibration spectra are analyzed using both combination differences and variational line lists. Two variational line lists were computed using the TROVE nuclear motion program: one is based on an ab initio potential energy surface (PES) while the other used a semi-empirical PES. Ab initio dipole moment surfaces are used in both cases. 95 energy levels with J=1−7 are determined from analysis of the experimental spectrum in the 5ν NH (red) region and 46 for 6ν NH (green) region. These levels span four vibrational bands in each of the two regions, associated with stretching overtones

A highly accurate ab initio dipole moment surface for the ground electronic state of water vapour for spectra extending into the ultraviolet

A new global and highly accurate ab initio dipole moment surface (DMS) for water vapour is presented. This DMS is based on a set of 17 628 multi-reference configuration interaction data points that were calculated with the aug-cc-pCV6Z basis set with the Douglas-Kroll-Hess Hamiltonian; tests are performed at several other levels of ab initio theory. This new "CKAPTEN" DMS improves agreement with recent experimental measurements compared with previous models that poorly predicted some bands in the infrared while also maintaining or improving on the agreement for all remaining strong lines. For high overtones located in both the visible and the near ultraviolet regions, our predicted intensities all lie within 10% of recent atmospheric observations. A crossing of energy levels in the ν1 fundamental and 2ν2 states is seen to offset transition intensities in the ν1 fundamental band; residual inaccuracies within the potential energy surface used is the cause of this problem

Exomol Molecular Line Lists XXX: a Complete High-accuracy Line List for Water

A new line list for H216O is presented. This line list, which is called POKAZATEL, includes transitions between rotational-vibrational energy levels up to 41 000 cm-1and is the most complete to date. The potential energy surface (PES) used for producing the line list was obtained by fitting a high-quality ab initio PES to experimental energy levels with energies of 41 000 cm-1and for rotational excitations up to J = 5. The final line list comprises all energy levels up to 41 000 cm-1and rotational angular momentum J up to 72. An accurate ab initio dipole moment surface was used for the calculation of line intensities and reproduces high-precision experimental intensity data with an accuracy close to 1 per cent. The final line list uses empirical energy levels, whenever they are available, to ensure that line positions are reproduced as accurately as possible. The POKAZATEL line list contains over 5 billion transitions and is available from the ExoMol website (www.exomol.com) and the CDS data base

High Accuracy ab initio Calculations of Rotational-Vibrational Levels of the HCN/HNC System

Highly accurate ab initio calculations of vibrational and rotational–vibrational energy levels of the HCN/HNC (hydrogen cyanide/hydrogen isocyanide) isomerising system are presented for several isotopologues. All-electron multireference configuration interaction (MRCI) electronic structure calculations were performed using basis sets up to aug-cc-pCV6Z on a grid of 1541 geometries. The ab initio energies were used to produce an analytical potential energy surface (PES) describing the two minima simultaneously. An adiabatic Born–Oppenheimer diagonal correction (BODC) correction surface as well as a relativistic correction surface were also calculated. These surfaces were used to compute vibrational and rotational–vibrational energy levels up to 25 000 cm–1 which reproduce the extensive set of experimentally known HCN/HNC levels with a root-mean-square deviation σ = 1.5 cm–1. We studied the effect of nonadiabatic effects by introducing opportune radial and angular corrections to the nuclear kinetic energy operator. Empirical determination of two nonadiabatic parameters results in observed energies up to 7000 cm–1 for four HCN isotopologues (HCN, DCN, H13CN, and HC15N) being reproduced with σ = 0.37 cm–1. The height of the isomerization barrier, the isomerization energy and the dissociation energy were computed using a number of models; our best results are 16 809.4, 5312.8, and 43 729 cm–1, respectively