Impact of ligand (OH) deformation on LuOH$^+$ rovibrational spectra

TL;DR

This study provides detailed ab initio calculations of LuOH$^+$ rovibrational spectra, including ligand deformation effects, to aid in precision searches for fundamental symmetry violations.

Contribution

It introduces a comprehensive computational approach that explicitly includes ligand deformation effects in the rovibrational analysis of LuOH$^+$, beyond the rigid-ligand approximation.

Findings

Ligand deformation reduces bending frequency by a few percent.

Increases the $l$-doubling constant $q$.

Predicts $ ext{Δ}E_{J=1} ext{≈} 24.9$–$26.4$ MHz for the first excited bending level.

Abstract

Triatomic cation $^{175}$LuOH$^+$, featuring near-degenerate, opposite-parity $l$-doublets, offers enhanced sensitivity to $\mathcal{P}$- and $\mathcal{T}$-violating interactions. We present \emph{ab initio} calculations of its electronic structure and rovibrational structure beyond the rigid-ligand approximation by explicitly including OH-ligand deformation together with bending and stretching motions. Potential-energy surfaces are computed at the relativistic coupled cluster level of theory. The nuclear Schr\"{o}dinger equation in Jacobi coordinates is solved by means of a coupled-channel expansion. Ligand deformation reduces the bending frequency by a few percent and increases the $l$-doubling constant $q$, while the stretching frequencies and rotational constants remain largely unchanged. For the first excited bending level, we predict $\Delta E_{J=1}=2q \approx 24.9$--$26.4$ MHz. These results establish LuOH$^+$ as a viable platform for precision searches for $\mathcal{CP}$-violating physics via the electron electric dipole moment and the nuclear magnetic quadrupole moment.