Rovibrational analysis of the water bending vibration in the mid-infrared spectrum of atmospherically significant N2–H2O complex

Springer, Sean; McElmurry, Blake A.; Wang, Z.; Leonov, Igor I.; Lucchese, Robert R.; Bevan, J. W.; Coudert, L. H.

doi:10.1016/j.cplett.2015.05.050

Cited by 6 publications

(1 citation statement)

References 26 publications

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“…Recently, we reported a rovibrational analysis of the water bending vibration in the most abundant pairwise complex in the atmosphere, N 2 -H 2 O [19] using a mode-hop free supersonic jet spectrometer. We now report assignment of the rovibrational transitions associated with tunneling states in the n 5 (water bending) vibration of the OC-H 2 O complex, the vibration associated with the n 2 bending vibration of the water monomer.…”

Section: Introductionmentioning

confidence: 99%

6.2 μm spectrum and 6-dimensional morphed potentials of OC-H2O

et al. 2018

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Rovibrational transitions associated with tunneling states in the n 5 (water bending) vibration of the OC-H 2 O complex have been recorded using a supersonic jet mode-hop free quantum cascade laser spectrometer at 6.2 µm. Analysis of the resulting spectra is facilitated by incorporating fits of previously recorded microwave and submillimeter data accounting for Coriolis coupling to confirm assignment of the n 5 vibration. The theoretical basis of morphing a 5-D frozen monomers potential was initially developed and then extended to two 6-D morphed potentials. A combination of these spectroscopic results and previous rovibrational data for the n 5 vibration in OC-D 2 O are then used to generate a 6-D morphed potential surface for the intermolecular and the water bending vibrations. An alternative 6-D morphed potential of the intermolecular and the

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Section: Introductionmentioning

confidence: 99%

6.2 μm spectrum and 6-dimensional morphed potentials of OC-H2O

et al. 2018

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Explicitly correlated ab initio potential energy surface and predicted rovibrational spectra for H2O–N2 and D2O–N2 complexes

Wang

Zhang

Zhai

et al. 2020

The Journal of Chemical Physics

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An ab initio intermolecular potential energy surface (PES) for the van der Waals complex of H2O–N2 that explicitly incorporates the intramolecular Q2 bending normal mode of the H2O monomer is presented. The electronic structure computations have been carried out at the explicitly correlated coupled cluster theory [CCSD(T)-F12] with an augmented correlation-consistent triple zeta basis set and an additional bond function. Analytic five-dimensional intermolecular PESs for ν2(H2O) = 0 and 1 are obtained by fitting to the multi-dimensional Morse/long-range potential function form. These fits to 40 890 points have the root-mean-square (rms) discrepancy of 0.88 cm−1 for interaction energies less than 2000.0 cm−1. The resulting vibrationally averaged PESs provide good representations of the experimental microwave and infrared data: for microwave transitions of H2O–N2, the rms discrepancy is only 0.0003 cm−1, and for infrared transitions of the A1 symmetry of the H2O(ν2 = 1 ← 0)–N2, the rms discrepancy is 0.001 cm−1. The calculated infrared band origin shifts associated with the ν2 bending vibration of water are 2.210 cm−1 and 1.323 cm−1 for H2O–N2 and D2O–N2, respectively, in good agreement with the experimental values of 2.254 cm−1 and 1.266 cm−1. The benchmark tests and comparisons of the predicted spectral properties are carried out between CCSD(T)-F12a and CCSD(T)-F12b approaches.

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Ab initio potential energy surface and microwave spectrum of the NH3–N2 van der Waals complex

Surin

Tarabukin

Hermanns

et al. 2020

The Journal of Chemical Physics

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We present a five-dimensional intermolecular potential energy surface (PES) of the NH3–N2 complex, bound state calculations, and new microwave (MW) measurements that provide information on the structure of this complex and a critical test of the potential. Ab initio calculations were carried out using the explicitly correlated coupled cluster [CCSD(T)-F12a] approach with the augmented correlation-consistent aug-cc-pVTZ basis set. The global minimum of the PES corresponds to a configuration in which the angle between the NH3 symmetry axis and the intermolecular axis is 58.7° with the N atom of the NH3 unit closest to the N2 unit, which is nearly parallel to the NH3 symmetry axis. The intermolecular distance is 7.01 a0, and the binding energy De is 250.6 cm–1. The bound rovibrational levels of the four nuclear spin isomers of the complex, which are formed when ortho/para (o/p)-NH3 combines with (o/p)-N2, were calculated on this intermolecular potential surface. The computed dissociation energies D0 are 144.91 cm−1, 146.50 cm−1, 152.29 cm−1, and 154.64 cm−1 for (o)-NH3–(o)-N2, (o)-NH3–(p)-N2, (p)-NH3–(o)-N2, and (p)-NH3–(p)-N2, respectively. Guided by these calculations, the pure rotational transitions of the NH3–N2 van der Waals complex were observed in the frequency range of 13–27 GHz using the chirped-pulse Fourier-transform MW technique. A complicated hyperfine structure due to three quadrupole 14N nuclei was partly resolved and examined for all four nuclear spin isomers of the complex. Newly obtained data definitively established the K values (the projection of the angular momentum J on the intermolecular axis) for the lowest states of the different NH3–N2 nuclear spin isomers.

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Rovibrational analysis of the water bending vibration in the mid-infrared spectrum of atmospherically significant N2–H2O complex

Cited by 6 publications

References 26 publications

6.2 μm spectrum and 6-dimensional morphed potentials of OC-H2O

6.2 μm spectrum and 6-dimensional morphed potentials of OC-H2O

Explicitly correlated ab initio potential energy surface and predicted rovibrational spectra for H2O–N2 and D2O–N2 complexes

Ab initio potential energy surface and microwave spectrum of the NH3–N2 van der Waals complex

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Rovibrational analysis of the water bending vibration in the mid-infrared spectrum of atmospherically significant N2–H2O complex

Cited by 6 publications

References 26 publications

6.2 μm spectrum and 6-dimensional morphed potentials of OC-H2O

6.2 μm spectrum and 6-dimensional morphed potentials of OC-H2O

Explicitly correlated ab initio potential energy surface and predicted rovibrational spectra for H2O–N2 and D2O–N2 complexes

Ab initio potential energy surface and microwave spectrum of the NH3–N2 van der Waals complex

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Product

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6.2 μm spectrum and 6-dimensional morphed potentials of OC-H2O

6.2 μm spectrum and 6-dimensional morphed potentials of OC-H2O