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\title{OXYGEN-ISOTOPE EFFECT ON THE NUCLEAR SPIN CONVERSION OF WATER MOLECULES}

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\author{\underline{\FirstName K. \LastName YAMAKAWA}}
\address{Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki, Japan}

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\author{\FirstName H. \LastName KAWABE,
  \FirstName K. \LastName YAMAGUCHI}
\address{Department of Physics, Gakushuin University, 1-5-1 Mejiro, Tokyo, Japan}

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\fancyhead[C]{{\footnotesize \textit{HRMS, 28th Colloquium, Dijon, France,
  Aug. 28 - Sept. 1, 2023}}}
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\category {3,6}
\begin{document}

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\index{Nuclear spin conversion}
\index{Matrix isolation}
\index{Low temperature}

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According to the resultant spin $I$ of two protons, water molecules are classified into two species: the ortho ($I = 1$) and para ($I = 0$) isomers. Because of the symmetry restriction, each isomer occupies specific rotational states. This coupling between the nuclear-spin and rotational states allows us to selectively monitor the isomers by rovibrational spectroscopy. The nuclear spin conversion between the isomers is extremely slow in the gas phase\footnote{\href{https://doi.org/10.1063/1.1633261}{doi:10.1063/1.1633261}, A. Miani and J. Tennyson, {\it J. Chem. Phys.\/}, {\bf 
120}, 2732--2739 (2004).}, but has been found to be much faster in condensed systems\footnote{\href{https://doi.org/10.1016/j.cplett.2009.08.071}{doi:10.1016/j.cplett.2009.08.071}, L. Abouaf-Marguin, A. M. Vasserot, C. Pardanaud, and X. Michaut, {\it Chem. Phys. Lett.\/}, {\bf 
480}, 82--85 (2009).}$^,$\footnote{\href{https://doi.org/10.1140/epjd/e2017-70642-8}{doi:10.1140/epjd/e2017-70642-8}, K. Yamakawa, S. Azami, and I. Arakawa, {\it  Eur. Phys. J. D\/}, {\bf 71}, 
70 (2017).}, whose mechanism is attracting interest. In the present study, we observed the conversion of H$_2$O trapped in solid Ar and investigated the oxygen-isotope effect. 

Our experimental apparatus mainly consists of an ultrahigh-vacuum (UHV) chamber, a Fourier transform infrared spectrometer, and a HgCdTe-detector compartment. After degassing, the pressure in the UHV chamber went below $1 \times 10^{-8}$ Pa. Liquid H$_2$O including the isotopologues of H$_2$$^{16}$O, H$_2$$^{17}$O, and H$_2$$^{18}$O was distilled by freeze-pump-thaw cycles. The gases of Ar and H$_2$O were mixed in a gas handling system and were condensed on a gold substrate cooled to $10.5$ K. Infrared absorption spectra were measured in the reflection configuration with the incident angle of $80^{\circ}$.

The absorption band of ortho (para) H$_2$O appeared in the range of $1595$ -- $1608$ ($1608$ -- $1625$) cm$^{-1}$ in an infrared spectrum after the sample deposition. The ortho band decayed with increasing time whereas the para one grew. This time evolution originated from the nuclear spin conversion from ortho to para. In addition, each band contained three components corresponding to H$_2$$^{16}$O, H$_2$$^{17}$O, and H$_2$$^{18}$O. Performing tri-gaussian fitting, we determined the integrated intensity of each component as a function of time and conversion rates of H$_2$$^{16}$O, H$_2$$^{17}$O, and H$_2$$^{18}$O. In the presentation, we will discuss the conversion mechanism, comparing these rates. 


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