1. Benchmarking of the Fock-space coupled-cluster method and uncertainty estimation
- Author
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Denis, Malika, Haase, Pi A. B., Mooij, Maarten C., Chamorro, Yuly, Aggarwal, Parul, Bethlem, Hendrick L., Boeschoten, Alexander, Borschevsky, Anastasia, Esajas, Kevin, Hao, Yongliang, Hoekstra, Steven, van Hofslot, Joost W. F., Marshall, Virginia R., Meijknecht, Thomas B., Timmermans, RobG. E., Touwen, Anno, Ubachs, Wim, Willmann, Lorenz, Yin, Yanning, Atoms, Molecules, Lasers, LaserLaB - Physics of Light, High-Energy Frontier, Precision Frontier, and Van Swinderen Institute for Particle Physics and G
- Subjects
Chemical Physics (physics.chem-ph) ,Atomic Physics (physics.atom-ph) ,Physics - Chemical Physics ,physics.chem-ph ,FOS: Physical sciences ,physics.atom-ph ,Physics - Atomic Physics - Abstract
We present an investigation of the performance of the relativistic multi-reference Fock-space coupled cluster (FSCC) method for predicting molecular hyperfine structure (HFS) constants, including a thorough computational study to estimate the associated uncertainties. In particular, we considered the $^{19}$F HFS constant in the ground and excited states of BaF. Due to a larger basis set dependence, the uncertainties on the excited state results (16-85%) were found to be significantly larger than those on the ground state constants ($\sim$2%). The ab initio values were compared to the recent experimental results, and good overall agreement within the theoretical uncertainties was found. This work demonstrates the predictive power of the FSCC method and the reliability of the established uncertainty estimates, which can be crucial in cases where the calculated property cannot be directly compared to experiment.
- Published
- 2022