Yachmenev, Andrey;
Yang, Guang;
Zak, Emil;
Yurchenko, Sergey;
Küpper, Jochen;
(2022)
The nuclear-spin-forbidden rovibrational transitions of water from first principles.
The Journal of Chemical Physics
10.1063/5.0090771.
(In press).
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Abstract
The water molecule occurs in two nuclear-spin isomers that differ by the value of the total nuclear spin of the hydrogen atoms, i.e., I = 0 for para-H2O and I = 1 for ortho-H2O. Spectroscopic transitions between rovibrational states of ortho and para water are extremely weak due to the tiny hyperfine nuclear-spin-rotation interaction of only ∼30 kHz and so far were not observed. We report the first comprehensive theoretical investigation of the hyperfine effects and ortho-para transitions in H216O due to nuclear-spin-rotation and spin-spin interactions. We also present the details of our newly developed general variational approach to the simulation of hyperfine effects in polyatomic molecules. Our results for water suggest that the strongest ortho-para transitions with room-temperature intensities on the order of 10−31 cm/molecule are about an order of magnitude larger than previously predicted values and should be detectable in the mid-infrared ν2 and near-infrared 2ν1 + ν2 and ν1 + ν2 + ν3 bands by current spectroscopy experiments.
| Type: | Article |
|---|---|
| Title: | The nuclear-spin-forbidden rovibrational transitions of water from first principles |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1063/5.0090771 |
| Publisher version: | https://doi.org/10.1063/5.0090771 |
| Language: | English |
| Additional information: | This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. |
| UCL classification: | UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy UCL > Provost and Vice Provost Offices > UCL BEAMS UCL |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10148742 |
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