A relativistic coupled-cluster treatment of magnetic hyperfine structure of the $X^2Π$ and $A^2Σ^+$ states of OH isotopologues
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| Formato: | Preprint |
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2025
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| author | Usov, D. P. Kozhedub, Y. S. Stolyarov, A. V. Skripnikov, L. V. Shabaev, V. M. Tupitsyn, I. I. |
| author_facet | Usov, D. P. Kozhedub, Y. S. Stolyarov, A. V. Skripnikov, L. V. Shabaev, V. M. Tupitsyn, I. I. |
| contents | $\textit{Ab initio}$ calculations of the parallel component of the magnetic dipole hyperfine structure (HFS) constant have been carried out for hydroxyl radical isotopologues ($^{16,17}$OH(D)) over the internuclear distance range $R \in [0.6, 1.8]$ Å. For the ground electronic state $X^2Π$, the HFS functions were evaluated for contributions induced by both oxygen and hydrogen nuclei. In addition, the hydrogen-induced HFS curve was calculated for the excited $A^2Σ^+$ state. The quantum-chemistry study employs a four-component relativistic coupled-cluster (CC) method, including excitations up to the triple level, namely: the contribution of triple-cluster amplitudes was studied both perturbatively (CCSD(T)) and through fully iterative calculations (CCSDT). The resulting oxygen- and hydrogen-induced HFS functions represent the most accurate and reliable theoretical predictions to date exhibiting excellent agreement with semiempirical curve for hydrogen-induced HFS derived from high-resolution spectroscopic data for the lowest vibrational levels ($v\in [0,2]$) of the electronic $X^2Π$ state. Vibrationally averaged $\textit{ab initio}$ values are consistent with experimental values within $1\%$ for all states considered. Furthermore, the internuclear distance range over which the HFS curves are defined has been extended beyond that of previous studies, thereby providing a robust foundation for accurate HFS treatments of higher-lying rovibrational levels of OH isotopologues within both adiabatic and non-adiabatic frameworks. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2509_20522 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | A relativistic coupled-cluster treatment of magnetic hyperfine structure of the $X^2Π$ and $A^2Σ^+$ states of OH isotopologues Usov, D. P. Kozhedub, Y. S. Stolyarov, A. V. Skripnikov, L. V. Shabaev, V. M. Tupitsyn, I. I. Chemical Physics Atomic and Molecular Clusters Computational Physics $\textit{Ab initio}$ calculations of the parallel component of the magnetic dipole hyperfine structure (HFS) constant have been carried out for hydroxyl radical isotopologues ($^{16,17}$OH(D)) over the internuclear distance range $R \in [0.6, 1.8]$ Å. For the ground electronic state $X^2Π$, the HFS functions were evaluated for contributions induced by both oxygen and hydrogen nuclei. In addition, the hydrogen-induced HFS curve was calculated for the excited $A^2Σ^+$ state. The quantum-chemistry study employs a four-component relativistic coupled-cluster (CC) method, including excitations up to the triple level, namely: the contribution of triple-cluster amplitudes was studied both perturbatively (CCSD(T)) and through fully iterative calculations (CCSDT). The resulting oxygen- and hydrogen-induced HFS functions represent the most accurate and reliable theoretical predictions to date exhibiting excellent agreement with semiempirical curve for hydrogen-induced HFS derived from high-resolution spectroscopic data for the lowest vibrational levels ($v\in [0,2]$) of the electronic $X^2Π$ state. Vibrationally averaged $\textit{ab initio}$ values are consistent with experimental values within $1\%$ for all states considered. Furthermore, the internuclear distance range over which the HFS curves are defined has been extended beyond that of previous studies, thereby providing a robust foundation for accurate HFS treatments of higher-lying rovibrational levels of OH isotopologues within both adiabatic and non-adiabatic frameworks. |
| title | A relativistic coupled-cluster treatment of magnetic hyperfine structure of the $X^2Π$ and $A^2Σ^+$ states of OH isotopologues |
| topic | Chemical Physics Atomic and Molecular Clusters Computational Physics |
| url | https://arxiv.org/abs/2509.20522 |