The nuclear-spin-forbidden rovibrational transitions of water from first principles

TL;DR

This paper presents a first-principles theoretical study of hyperfine effects and nuclear-spin-forbidden rovibrational transitions in water, revealing that some weak transitions are stronger than previously thought and potentially detectable with current spectroscopy.

Contribution

The authors develop a new variational approach to simulate hyperfine effects in polyatomic molecules and apply it to water, providing the first detailed theoretical predictions of nuclear-spin-forbidden transitions.

Findings

Hyperfine effects in water are larger than previously predicted.

Certain ortho-para transitions have detectable intensities at room temperature.

Theoretical predictions suggest these transitions can be observed in specific infrared bands.

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-H$_2$O and $I=1$ for ortho-H$_2$O. Spectroscopic transitions between rovibrational states of ortho and para water are extremely weak due to the tiny hyperfine nuclear-spin-rotation interaction of only $\sim30$ kHz and so far were not observed. We report the first comprehensive theoretical investigation of the hyperfine effects and ortho-para transitions in H$_2$$^{16}$O 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 $\nu_2$ and near-infrared $2\nu_1+\nu_2$ and $\nu_1+\nu_2+\nu_3$ bands by current spectroscopy experiments.