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Water vapour is known to absorb radiation from the microwave region to the blue part of the visible spectrum with decreasing efficiency. Ab initio approaches to model individual absorption lines of the gaseous water molecule predict absorption lines up to its dissociation limit at 243 nm.We present the first evidence of water vapour absorption near 363 nm from field measurements using data from multi-axis differential optical absorption spectroscopy (MAX-DOAS) and long-path (LP)-DOAS measurements. The identification of the absorptions was based on the recent POKAZATEL line list by Polyansky et al. (2017). For MAX-DOAS measurements, we observed absorption by water vapour in an absorption band around 363 nm with optical depths of up to 2 × 10−3. The retrieved column densities from 2 months of measurement data and more than 2000 individual observations at different latitudes correlate well with simultaneously measured well-established water vapour absorptions in the blue spectral range from 452 to 499 nm (R2 = 0.89), but the line intensities at around 363 nm are underestimated by a factor of 2.6  ±  0.5 by the ab initio model. At a spectral resolution of 0.5 nm, we derive a maximum cross section value of 2.7 × 10−27 cm2 molec−1 at 362.3 nm. The results were independent of the used literature absorption cross section of the O4 absorption, which overlays this water vapour absorption band. Also water vapour absorption around 376 nm was identified. Below 360 nm no water vapour absorption above 1.4 × 10−26 cm2 molec−1 was observed. The newly found absorption can have a significant impact on the spectral retrievals of absorbing trace-gas species in the spectral range around 363 nm. Its effect on the spectral analysis of O4, HONO and OClO is discussed.

Transition intensities for small molecules such as water and CO2 can now be computed with such high accuracy that they are being used to systematically replace measurements in standard databases. These calculations use high-accuracy ab initio dipole moment surfaces and wave functions from spectroscopically determined potential energy surfaces (PESs). Here, an extra high-accuracy PES of the water molecule (H216O) is produced starting from an ab initio PES which is then refined to empirical rovibrational energy levels. Variational nuclear motion calculations using this PES reproduce the fitted energy levels with a standard deviation of 0.011 cm−1, approximately three times their stated uncertainty. The use of wave functions computed with this refined PES is found to improve the predicted transition intensities for selected (problematic) transitions. A new room temperature line list for H216O is presented. It is suggested that the associated set of line intensities is the most accurate available to date for this species. This article is part of the theme issue 'Modern theoretical chemistry'.

In order to promote the development of the passive DOAS technique the Multi Axis DOAS – Comparison campaign for Aerosols and Trace gases (MAD-CAT) was held at the Max Planck Institute for Chemistry in Mainz, Germany, from June to October 2013. Here, we systematically compare the differential slant column densities (dSCDs) of nitrous acid (HONO) derived from measurements of seven different instruments. We also compare the tropospheric difference of SCDs (delta SCD) of HONO, namely the difference of the SCDs for the non-zenith observations and the zenith observation of the same elevation sequence. Different research groups analysed the spectra from their own instruments using their individual fit software. All the fit errors of HONO dSCDs from the instruments with cooled large-size detectors are mostly in the range of 0.1 to 0.3  ×  1015 molecules cm−2 for an integration time of 1 min. The fit error for the mini MAX-DOAS is around 0.7  ×  1015 molecules cm−2. Although the HONO delta SCDs are normally smaller than 6  ×  1015 molecules cm−2, consistent time series of HONO delta SCDs are retrieved from the measurements of different instruments. Both fits with a sequential Fraunhofer reference spectrum (FRS) and a daily noon FRS lead to similar consistency. Apart from the mini-MAX-DOAS, the systematic absolute differences of HONO delta SCDs between the instruments are smaller than 0.63  ×  1015 molecules cm−2. The correlation coefficients are higher than 0.7 and the slopes of linear regressions deviate from unity by less than 16 % for the elevation angle of 1°. The correlations decrease with an increase in elevation angle. All the participants also analysed synthetic spectra using the same baseline DOAS settings to evaluate the systematic errors of HONO results from their respective fit programs. In general the errors are smaller than 0.3  ×  1015 molecules cm−2, which is about half of the systematic difference between the real measurements.The differences of HONO delta SCDs retrieved in the selected three spectral ranges 335–361, 335–373 and 335–390 nm are considerable (up to 0.57  ×  1015 molecules cm−2) for both real measurements and synthetic spectra. We performed sensitivity studies to quantify the dominant systematic error sources and to find a recommended DOAS setting in the three spectral ranges. The results show that water vapour absorption, temperature and wavelength dependence of O4 absorption, temperature dependence of Ring spectrum, and polynomial and intensity offset correction all together dominate the systematic errors. We recommend a fit range of 335–373 nm for HONO retrievals. In such fit range the overall systematic uncertainty is about 0.87  ×  1015 molecules cm−2, much smaller than those in the other two ranges. The typical random uncertainty is estimated to be about 0.16  ×  1015 molecules cm−2, which is only 25 % of the total systematic uncertainty for most of the instruments in the MAD-CAT campaign. In summary for most of the MAX-DOAS instruments for elevation angle below 5°, half daytime measurements (usually in the morning) of HONO delta SCD can be over the detection limit of 0.2  ×  1015 molecules cm−2 with an uncertainty of  ∼  0.9  ×  1015 molecules cm−2.

This work is devoted to estimation of the additional absorption of millimeter and submillimeter wavelengths in water vapor arising from collisional interaction of molecules due to the induced dipole moment. Absorption is modeled on the basis of ab initio data on the magnitude of the water molecule dipole moment at high densities, and common knowledge of the water vapor absorption spectrum. Using the model developed, we obtained a simple analytical expression for the absorption coefficient as a function of temperature, pressure, and frequency. Comparison of the results with known experimental data leads to the conclusion that in the range of pressures and temperatures typical of water vapor in the Earth’s atmosphere this type of absorption is negligible compared with the absorption arising due to association or dimerization of the water vapor molecules.

The quantum mechanical description of isomerization is based on bound eigenstates of the molecular potential energy surface. For the near-minimum regions there is a textbook-based relationship between the potential and eigenenergies. Here we show how the saddle point region that connects the two minima is encoded in the eigenstates of the model quartic potential and in the energy levels of the [H, C, N] potential energy surface. We model the spacing of the eigenenergies with the energy dependent classical oscillation frequency decreasing to zero at the saddle point. The eigenstates with the smallest spacing are localized at the saddle point. The analysis of the HCN ↔ HNC isomerization states shows that the eigenstates with small energy spacing relative to the effective ( v 1 , v 3 , ℓ ) bending potentials are highly localized in the bending coordinate at the transition state. These spectroscopically detectable states represent a chemical marker of the transition state in the eigenenergy spectrum. The method developed here provides a basis for modeling characteristic patterns in the eigenenergy spectrum of bound states.

We present a comprehensive theoretical study of the ionization potentials of the MF (M= Ca, Sr, Ba) molecules using the state-of-the-art relativistic coupled cluster approach with single, double, and perturbative triple excitations (CCSD(T)). We have further corrected our results for the higher order excitations (up to full triples) and the QED self energy and vacuum polarisation contributions. We have performed an extensive investigation of the effect of the various computational parameters on the calculated ionisation potentials, which allowed us to assign realistic uncertainties on our predictions. For CaF and BaF, where precise experiments are available, our predictions are in excellent agreement with the measured values. In case of SrF, we provide a new accurate prediction of the ionisation potential that deviates from the available experimental data, motivating further experimental investigations.

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 \\(\\permil\\) 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 \\(\\permil\\) level. This set of highly accurate intensities can provide an intrinsic reference for reducing biases in future measurements of spectroscopic peak areas.

Transition intensities for small molecules such as water and CO₂ can now be computed with such high accuracy that they are being used to systematically replace measurements in standard databases. These calculations use high-accuracy ab initio dipole moment surfaces and wave functions from spectroscopically determined potential energy surfaces (PESs). Here, an extra high-accuracy PES of the water molecule 16 (H₂¹₆O) is produced starting from an ab initio PES which is then refined to empirical rovibrational energy levels. Variational nuclear motion calculations using this PES reproduce the fitted energy levels with a standard deviation of 0.011 cm⁻¹, approximately three times their stated uncertainty. The use of wave functions computed with this refined PES is found to improve the predicted transition intensities for selected (problematic) transitions. A new room temperature line list for H₂¹₆O is presented. It is suggested that the associated set of line intensities is the most accurate available to date for this species. This article is part of the theme issue 'Modern theoretical chemistry'.

Water vapour is known to absorb radiation from the microwave region to the blue part of the visible spectrum with decreasing efficiency. Ab initio approaches to model individual absorption lines of the gaseous water molecule predict absorption lines up to its dissociation limit at 243nm. We present the first evidence of water vapour absorption near 363nm from field measurements using data from multi-axis differential optical absorption spectroscopy (MAX-DOAS) and long-path (LP)-DOAS measurements. The identification of the absorptions was based on the recent POKAZATEL line list by Polyansky et al. (2017). For MAX-DOAS measurements, we observed absorption by water vapour in an absorption band around 363nm with optical depths of up to 2 × 10-3. The retrieved column densities from 2 months of measurement data and more than 2000 individual observations at different latitudes correlate well with simultaneously measured well-established water vapour absorptions in the blue spectral range from 452 to 499nm (R2 = 0.89), but the line intensities at around 363nm are underestimated by a factor of 2.6 ± 0.5 by the ab initio model. At a spectral resolution of 0.5nm, we derive a maximum cross section value of 2.7 × 10-27cm2molec-1 at 362.3nm. The results were independent of the used literature absorption cross section of the O4 absorption, which overlays this water vapour absorption band. Also water vapour absorption around 376nm was identified. Below 360nm no water vapour absorption above 1.4 × 10-26cm2molec-1 was observed. The newly found absorption can have a significant impact on the spectral retrievals of absorbing trace-gas species in the spectral range around 363nm. Its effect on the spectral analysis of O4, HONO and OClO is discussed.

The ionization potential (IP) of radium monofluoride (RaF) was measured to be 4.969(2)[10] eV, revealing a relativistic enhancement in the series of alkaline earth monofluorides. The results are in agreement with a relativistic coupled-cluster prediction of 4.969[7] eV, incorporating up to quantum electrodynamics corrections. Using the same computational methodology, an improved calculation for the dissociation energy (\\(D_{0}\\)) of 5.54[5] eV is presented. This confirms that radium monofluoride joins the small group of diatomic molecules for which \\(D_{0}>\\mathrm{IP}\\), paving the way for precision control and interrogation of its Rydberg states.