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\title{CHARACTERISATION OF THE GROUND AND LOW-LYING EXCITED STATES OF MgO$^{+}$ BY PFI-ZEKE PHOTOELECTRON SPECTROSCOPY}

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\author{\underline{\FirstName JOEL R. \LastName SCHMITZ},
  \FirstName CARLA \LastName KREIS, \FirstName FR\'{E}D\'{E}RIC \LastName MERKT}
\address{Department of Chemistry and Applied Biosciences, ETH Z\"{u}rich, Z\"{u}rich, Switzerland}

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\fancyhead[C]{{\footnotesize \textit{HRMS, 28th Colloquium, Dijon, France,
  Aug. 28 - Sept. 1, 2023}}}
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We report on the characterisation of the rovibrational structure of the ground and first excited electronic states of MgO$^{+}$ by high-resolution pulsed-field ionization zero-kinetic-energy  (PFI-ZEKE) photoelectron spectroscopy. Rotationally cold ($T_{\rm rot}=5$K) MgO molecules in the X~$^{1}$$\Sigma$$^{+}$ ($v = 0-2$) levels were generated in a supersonic expansion of a 0.1\% N$_{2}$O:He gas mixture following laser ablation off a magnesium (Mg) rod [1]. The rovibrational ionization thresholds corresponding to both spin-orbit components ($\Omega=\frac{1}{2},\frac{3}{2}$)  of the X$^{+}$ $^{2}$$\Pi$$_{\Omega}$ ($v^{+} = 0 -10$) states as well as to the first excited A$^{+}$ $^{2}$$\Sigma$$_{\frac{1}{2}}$$^{+}$ ($v^{+} = 0 -10$) state were reached in a resonant 1+1$^{\prime}$ two-photon excitation sequence via the rovibrational levels of the F~$^{1}$$\Pi$, E~$^{1}$$\Sigma$$^{+}$, G~$^{1}$$\Pi$ and 3~$^{3}\Pi_{2}$ intermediate levels of MgO studied previously by Breckenridge and coworkers [2,3]. Our new results include accurate values for the adiabatic ionization energy of MgO and for the dissociation energies of the MgO X~$^{1}$$\Sigma$$^{+}$ and MgO$^{+}$ X$^{+}$ $^{2}$$\Pi$$_{\Omega}$ and A$^+~^{2}\Sigma^{+}_{\frac{1}{2}}$ states. This work is carried out in the context of our studies of the rovibrational structure of doubly charged dications by high-resolution PFI-ZEKE spectroscopy of singly-charged cations following the approach recently taken to characterise the ground state of the thermodynamically stable dication MgAr$^{2+}$ [4]. The talk will present a roadmap towards characterising the ground state of MgO$^{2+}$ by resonant multiphoton excitation via  electronically excited states of MgO$^{+}$. The experiments will reveal whether MgO$^{2+}$ is thermodynamically stable as predicted in Ref. [5] or metastable as predicted in Ref. [6].\hfill \break


\begin{footnotesize}

\noindent [1] T.D. Persinger, D.J. Frohman, W.M. Fawzy and M.C. Heaven, J. Phys. Chem. \textbf{153}, 054308 (2020).

\noindent [2] J. Wang and W.H. Breckenridge, J. Chem. Phys. \textbf{124}, 124308 (2006).

\noindent [3] D. Bellert, K.L. Burns, N.T. Van-Oanh, J. Wang and W. Breckenridge, Chem. Phys. Lett. \textbf{381}, 381--384 (2003).

\noindent [4] D. Wehrli, M. G\'{e}n\'{e}vriez and F. Merkt, Phys. Chem. Chem. Phys. \textbf{23}, 10978--10987 (2021).

\noindent [5] R. Linguerri, M. Hochlaf, M.C. Bacchus-Montabonel and M. Desouter-Lecomte, Phys. Chem. Chem. Phys. \textbf{15}, 824--831 (2013).

\noindent [6] M. Kolbuszewski and J.S. Wright, Chem. Phys. Lett. \textbf{218}, 338--342 (1994).
\end{footnotesize}	 

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