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CO2 and CO are listed as molecules 2 and 5, respectively, in the HITRAN database, with the former being the most important greenhouse gas in the Earth’s atmosphere and the latter being the second most common molecule in the Universe after H2. Thus knowing the line intensities of both CO2 and CO with low uncertainty has wideranging scientific importance. Until recently only the effective Hamiltonian and Dipole Moment Surfaces(DMS) were used to calculate line positions and intensities of these molecules. However, there is a theoretical line list based on variational calculations using a fitted potential energy surface (PES) and an ab initio DMS which has been determined recently1 and which givesCO2 line intensities that are accurate to within a few percent. In this work we attempt to improve and experimentally validate the accuracy of the predicted CO2 line intensities at the sub-percent level. However, only a few lines belonging to four CO2 bands have thus far been measured at this level of uncertainty. We performed ab initio calculations of the PES and DMS of CO2 at the all-electron MRCI level of theory using MOLPRO and an aug-cc-pcQz basis set. Values for about 2000 geometries were calculated with energies up to 20 000 cm−1 above the minimum. We fitted an analytical surface to these DMS points and calculated intensities using the excellent PES of Ref. 1 and our DMS using the variational triatomic nuclear motion program DVR3D2.We will present a comparison of our calculated line intensities with several measured lines in the four above-mentioned bands. This comparison between theory and experiments demonstrates that sub-percent relative uncertainty in the predicted intensities of CO2 lines has been achieved. The results of similarly accurate calculations on CO will also be presented.

Recommendations of an IUPAC Task Group, formed in 2011 on “Intensities and line shapes in high-resolution spectra of water isotopologues from experiment and theory”(Project No. 2011-022-2-100), on line profiles of isolated high-resolution rotational-vibrational transitions perturbed by neutral gas-phase molecules are presented. The well-documented inadequacies of the Voigt profile, used almost universally by databases and radiative-transfer codes to represent pressure effects and Doppler broadening in isolated vibrational-rotational and pure rotational transitions of the water molecule, have resulted in the development of a variety of alternative line profile models. These models capture more of the physics of the influence of pressure on line shapes but, in general, at the price of greater complexity. The Task Group recommends that the partially-Correlated quadratic-Speed-Dependent Hard-Collision profile should be adopted as the appropriate model for high-resolution spectroscopy. For simplicity this should be called the Hartmann–Tran profile (HTP). This profile is sophisticated enough to capture the various collisional contributions to the isolated line shape, can be computed in a straightforward and rapid manner, and reduces to simpler profiles, including the Voigt profile, under certain simplifying assumptions. For further details see: J. Tennyson et al, Pure Appl. Chem., 2014, in press.

High-temperature water linelists for three water isotopologues -H216O,H217O and H218O are calculated using the newly developed potential energy surfaces (PESs) and the high-quality dipole moment surface (DMS)1. ForH216O, a PES accurate up to 40 000 cm−1 was developed and the energy levels cutoff up to 40 000 cm−1 was used. The lines for all the levels up to J =72 are computed.The accuracy of the PES is an order of magnitude better than the one used for the BT2 linelist2.For the two minor isotopologues, less extensive linelists are calculated, which coincide in highest J ≤ 50 and energy levels up to 30 000 cm−1, with the parameters used for the BT2 linelist. A newly-developed method for calculating the PES of isotopologues is used which gives the same level of accuracy for H217O and H218O as obtained for known levels of H216O even when these levels are yet unknown experimentally for the minor isotopologue.

State-of-the-art experiments and calculations are used to record and assign the data obtained in the weakly absorbing blue energy region of the H2O spectrum. Continuous-wave cavity ringdown absorption spectroscopy with Doppler resolution is used to probe the range from 25 195 to 25 470 cm(-1) with an absorption sensitivity of similar to 1 parts per 10(9) (ppb)/cm. 62 lines of the polyad nu(OH)=8 are reported, of which 43 are assigned using variational nuclear calculations. The study includes absorption line intensities (in the range of 10(-28)-10(-26) cm/molecule) for all lines and self-broadening pressure coefficient for a few lines. The newly obtained energy levels are also reported. (c) 2005 American Institute of Physics.

Line parameters for water vapour in natural abundance have recently been determined for the 9250-13 000 cm(-1) region [M.-F. Wrienne, A. Jenouvrier, C. Hermans, A.C. Vandaele, M. Carleer, C. Clerbaux, P.-F. Coheur, R. Colin, S. Fally, M. Bach, J. Quant. Spectrosc. Radiat. Transfer 82 (2003) 99] and the 13 000-26 000 cm(-1) region [P.-F. Coheur, S. Fally, M. Carleer, C. Clerbaux, R. Colin, A. Jenouvrier, M.-F. Wrienne, C. Hermans, A.C. Vandaele, J. Quant. Spectrosc. Radial. Transfer 74 (2002) 493] using a high-resolution Fourier-transform spectrometer with a long-path absorption cell. These spectra are analysed using several techniques including variational line lists and assignments made. In total, over 15 000 lines were assigned to transitions involving more than 150 exited vibrational states of (H2O)-O-16. Twelve new vibrational band origins are determined and estimates for a further 16 are presented. (c) 2005 Elsevier Inc. All rights reserved.

Equilibrium structures are fundamental entities in molecular sciences. They can be inferred from experimental data by complicated inverse procedures which often rely on several assumptions, including the Born-Oppenheimer approximation. Theory provides a direct route to equilibrium geometries. A recent high-quality ab initio semiglobal adiabatic potential-energy surface (PES) of the electronic ground state of water, reported by Polyansky [ ibid. 299, 539 (2003)] and called CVRQD here, is analyzed in this respect. The equilibrium geometries resulting from this direct route are deemed to be of higher accuracy than those that can be determined by analyzing experimental data. Detailed investigation of the effect of the breakdown of the Born-Oppenheimer approximation suggests that the concept of an isotope-independent equilibrium structure holds to about 3x10(-5) A and 0.02 degrees for water. The mass-independent [Born-Oppenheimer (BO)] equilibrium bond length and bond angle on the ground electronic state PES of water is r(e)(BO)=0.957 82 A and theta(e)(BO)=104.48(5)degrees, respectively. The related mass-dependent (adiabatic) equilibrium bond length and bond angle of (H2O)-O-16 is r(e)(ad)=0.957 85 A and theta(e)(ad)=104.50(0)degrees, respectively, while those of (D2O)-O-16 are r(e)(ad)=0.957 83 A and theta(e)(ad)=104.49(0)degrees. Pure ab initio prediction of J=1 and 2 rotational levels on the vibrational ground state by the CVRQD PESs is accurate to better than 0.002 cm(-1) for all isotopologs of water considered. Elaborate adjustment of the CVRQD PESs to reproduce all observed rovibrational transitions to better than 0.05 cm(-1) (or the lower ones to better than 0.0035 cm(-1)) does not result in noticeable changes in the adiabatic equilibrium structure parameters. The expectation values of the ground vibrational state rotational constants of the water isotopologs, computed in the Eckart frame using the CVRQD PESs and atomic masses, deviate from the experimentally measured ones only marginally, especially for A(0) and B-0. The small residual deviations in the effective rotational constants are due to centrifugal distortion, electronic, and non-Born-Oppenheimer effects. The spectroscopic (nonadiabatic) equilibrium structural parameters of (H2O)-O-16, obtained from experimentally determined A(0)(') and B-0(') rotational constants corrected empirically to obtain equilibrium rotational constants, are r(e)(sp)=0.957 77 A and theta(e)(sp)=104.48 degrees.

An emission spectrum of hot water with a temperature of about 3000 K is obtained using an oxy-acetylene torch. This spectrum contains a very large number of transitions. The spectrum, along with previous cooler laboratory emission spectra and an absorption spectrum recorded from a sunspot, is analyzed in the 500-2000 cm(-1) region. Use of a calculated variational linelist for water allows significant progress to be made on assigning transitions involving highly excited vibrational and rotational states. In particular emission from rotationally excited states up to J=42 and vibrational levels with up to eight quanta of bending motion are assigned.

The DVR3D program suite calculates energy levels, wavefunctions, and where appropriate dipole transition moments, for rotating and vibrating triatomic molecules. Potential energy and, where necessary, dipole surfaces must be provided. Expectation values of geometrically defined functions can be calculated, a feature which is particularly useful for fitting potential energy surfaces. The programs use an exact (within the Born–Oppenheimer approximation) Hamiltonian and offer a choice of Jacobi or Radau internal coordinates and several body-fixed axes. Rotationally excited states are treated using an efficient two-step algorithm. The programs uses a Discrete Variable Representation (DVR) based on Gauss–Jacobi and Gauss–Laguerre quadrature for all 3 internal coordinates and thus yields a fully point-wise representation of the wavefunctions. The vibrational step uses successive diagonalisation and truncation which is implemented for a number of possible coordinate orderings. The rotational, expectation value and transition dipole programs exploit the savings offered by performing integrals on a DVR grid. The new version has been rewritten in FORTRAN 90 to exploit the dynamic array allocations and the algorithm for dipole and spectra calculations have been substantially improved. New modules allow the z-axis to be embedded perpendicular to the plane of the molecule and for the calculation of expectation values.

Fourier transform emission spectra of D2O vapor were recorded at a temperature of 1500 °C in the wavenumber range 380–1880 cm–1. 15 346 lines were measured, of which the majority were identified as belonging to D2O. The spectrum was analyzed using variational nuclear motion calculations based on spectroscopically determined potential-energy surfaces. Initial assignments were made using a potential surface obtained by fitting a high accuracy ab initio potential. The new assignments were used to refine the potential surface, resulting in additional assignments. A total of 6400 D2O transitions were assigned and 2144 new D2O energy levels were obtained. Transitions involving the 42 and 52 bending states, with band origins of 4589.30 (±0.02) and 5679.6 (±0.1) cm–1, respectively, were assigned for the first time.

Water is the single most important molecule for models of the earth's atmosphere but line parameters for water, particularly at shorter wavelengths, are difficult to measure reliably. We suggest that the most reliable way of generating water line parameters is to combine data obtained from a variety of sources, thereby separating line parameter determination into results for strong lines, for weak lines and for isotopically substituted water. Theoretical considerations which are addressed include line assignments and labeling of energy levels and the prospects of a full theoretical solution to the water vapor problem. Particular attention is paid to strong line absorption intensities in the near-infrared where recent studies have given significantly different results. The experimental data used to construct the ESA-WVR linelist (J. Mol. Spectrosc. 208 (2001) 32) is re-analyzed with a focus on effects due to pressure determination in the cell, subtraction of the baseline and parameterization of the line profiles. A preliminary re-analysis suggests that the line intensities given by the ESA-WVR study should be closer to those of Brown et al. (J. Mol. Spectrosc. 212 (2002) 57) used in the HITRAN. This shows the vital importance of validating the data for water by independent means. (C) 2003 Elsevier Ltd. All rights reserved.

A total of 7923 transitions previously derived from long pathlength, Fourier transform spectra of pure water vapor (Schermaul et al., J. Mol. Spectrosc. 211 (2002) 169) have been refitted and reanalyzed using a newly calculated variational linelist. Of these, 6600 lines are weaker than 1 × 10−24 cm/molecule, for which reliable intensities are obtained. These weak lines include 1082 lines, largely due to H216O, which have not been previously observed. A total of 7156 lines were assigned resulting in 329 new energy levels for H216O spread over 32 vibrational levels. Estimates are also given for the band origins of the (022), (140), and (051) vibrational states.

Fourier transform emission spectra were recorded using a mixture of H2O and D2O at a temperature of 1500 °C. The spectra were recorded in three overlapping sections and cover the wavenumber range 1800–3932 cm−1. This spectrum is analyzed together with a previously reported one spanning the 380–2190 cm−1 range [Parekunnel et al., J. Mol. Spectrosc. 2001 (28) 101]. This analysis leads to 4409 newly assigned HDO emission lines. This work particularly extends data on the (200) and (120) states of HDO for which newly determined energy levels are presented.

A potential energy surface for the major isotopomer of water is constructed by fitting to observed vibration–rotation energy levels of the system using the exact kinetic energy operator nuclear motion program DVR3D. The starting point for the fit is the ab initio Born–Oppenheimer surface of Partridge and Schwenke [J. Chem. Phys. 106, 4618 (1997)] and corrections to it: both one- and two-electron relativistic effects, a correction to the height of the barrier to linearity, allowance for the Lamb shift and the inclusion of both adiabatic and nonadiabatic non-Born–Oppenheimer corrections. Fits are made by scaling the starting potential by a morphing function, the parameters of which are optimized. Two fitted potentials are presented which only differ significantly in their treatment of rotational nonadiabatic effects. Energy levels up to 25 468 cm–1 with J = 0, 2, and 5 are fitted with only 20 parameters. The resulting potentials predict experimentally known levels with J≤10 with a standard deviation of 0.1 cm–1, and are only slightly worse for J = 20, for which rotational nonadiabatic effects are significant. The fits showed that around 100 known energy levels are probably the result of misassignments. Analysis of misassigned levels above 20 000 cm–1 leads to the reassignment of 23 transitions.

The spectrum of water vapor is of fundamental importance for a variety of processes, including the absorption and retention of sunlight in Earth's atmosphere. Therefore, there has long been an urgent need for a robust and accurate predictive model for this spectrum. In our work on the high-resolution spectrum of water, we report first-principles calculations that approach experimental accuracy. To achieve this, we performed exceptionally large electronic structure calculations and considered a variety of effects, including quantum electrodynamics, which have routinely been neglected in studies of small many-electron molecules. The high accuracy of the resulting ab initio procedure is demonstrated for the main isotopomers of water.

The infrared spectrum of sunspots is analyzed in the H-band region (55406997 cm-1) with the aid of a new, hot (T = 1800 K) laboratory emission spectrum of water covering 48787552 cm-1. There are 682 lines in the sunspot spectrum and 5589 lines in the laboratory spectrum assigned quantum numbers corresponding to transitions due to H216O using a combination of previously known experimental energy levels for water and variational line lists. A further 201 unassigned lines common to both spectra can also be associated with water.

The factors that need to be taken into account to achieve spectroscopic accuracy for triatomic molecules are considered focusing on H3+ and water as examples. The magnitude of the adiabatic and non-adiabatic corrections to the Born–Oppenheimer approximation is illustrated for both molecules, and methods of including them ab initio are discussed. Electronic relativistic effects are not important for H3+, but are for water for which the magnitude of the various effects is discussed. For H3+ inclusion of rotational non-adiabatic effects means that levels can be generated to an accuracy approaching 0.01 cm−1; for water the error is still dominated by the error in the correlation energy in the electronic structure calculation. Prospects for improving this aspect of the calculation are discussed.

New Fourier transform spectra of water vapor are presented in the range 6500–16 400 cm−1 obtained using pathlengths of up to 800 m and long integration times. These spectra have a significantly higher signal-to-noise than previous measurements in this wavenumber range. Wavenumbers, absolute intensities and self-broadening coefficients, all with associated uncertainties, are presented for 3604 lines in the region 13 200–15 000 cm−1. Analysis of these lines using variational linelists, along with other unassigned lines from previous studies, has been conducted. This leads to 952 new line assignments to transitions involving 35 different vibrational states of H216O. A smaller number of lines are assigned to H218O and H217O.

Fourier transform emission spectra were recorded using a mixture of H2O and D2O at a temperature of 1500 degreesC. The spectra were recorded in three overlapping sections and cover the wavenumber range 380-2190 cm(-1). A total of 22106 lines were measured, of which 60% are thought to belong to HDO. A total of 6430 FIDO transition,, are assigned, including the first transitions to the (040) vibrational state, with a term value of 5420.042 cm(-1). A total of 1536 new energy levels of HDO belonging to the (000), (010) (020), (030), and (040) stated are presented, significantly extending the degree of rotational excitation compared to previous studies. (C) 2001 Elsevier Science.

Experimentally derived energy levels are presented for 12 248 vibration–rotation states of the H2 16O isotopomer of water, more than doubling the number in previous, disparate, compilations. For each level an error and reference to source data is given. The levels have been checked using energy levels derived from sophisticated variational calculations. These levels span 107 vibrational states including members of all polyads up to and including 8v. Band origins, in some cases estimates, are presented for 101 vibrational modes.

Quantum beat spectroscopy is combined with triple-resonance vibrational overtone excitation to measure the Stark coefficients (SCs) of the water molecule for 28 rovibrational levels lying from 27 600 to 41 000 cm−1. These data provide a stringent test for assessing the accuracy of the available potential energy surfaces (PESs) and dipole moment surfaces (DMSs) of this benchmark molecule in this energy region, which is inaccessible by direct absorption. SCs, calculated using the combination of a high accuracy, spectroscopically determined PES and a recent ab initio DMS, are within the 1% accuracy of available experimental data for levels below 25 000 cm−1 , and within 4.5% for coefficients associated with levels up to 35000 cm−1. However, the error in the computed coefficients is over 60% for the very high rovibrational states lying just below the lowest dissociation threshold, due, it seems, to lack of a high accuracy PES in this region. The comparative analysis sug-gests further steps, which may bring the theoretical predictions closer to the experimental accuracy.