Benchmarking of the Fock space coupled cluster method and uncertainty estimation: Magnetic hyperfine interaction in the excited state of BaF
Malika Denis, Pi A. B. Haase, Maarten C. Mooij, Yuly Chamorro, Parul Aggarwal, Hendrick L. Bethlem, Alexander Boeschoten, Anastasia Borschevsky, Kevin Esajas, Y… 展开作者
Malika Denis, Pi A. B. Haase, Maarten C. Mooij, Yuly Chamorro, Parul Aggarwal, Hendrick L. Bethlem, Alexander Boeschoten, Anastasia Borschevsky, Kevin Esajas, Yongliang Hao, Steven Hoekstra, Joost W. F. van Hofslot, Virginia R. Marshall, Thomas B. Meijknecht, RobG. E. Timmermans, Anno Touwen, Wim Ubachs, Lorenz Willmann, Yanning Yin
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.
Global isotopic analysis of hyperfine-resolved rotational spectroscopic data for barium monofluoride, BaF
Pomona College（波莫纳学院）；Gottfried-Wilhelm-Leibniz-Universität, Institut für Physikalische Chemie and Elektrochemie, Lehrgebiet A（哥特弗里德·威廉·莱布尼茨大学，物理化学与电化学研究所，A教学组）
We report an experimental investigation on the Doppler-free saturated absorption spectroscopy of buffer-gas-cooled Barium monofluoride (BaF) molecules in a 4~K cryogenic cell. The obtained spectra with a resolution of 19~MHz, much smaller than previously observed in absorption spectroscopy, clearly resolve the hyperfine transitions. Moreover, we use these high-resolution spectra to fit the hyperfine splittings of excited $A(v=0)$ state and find the hyperfine splitting of the laser-cooling-relevant $A^2Π_{1/2}(v=0, J=1/2, +)$ state is about 18 MHz, much higher than the previous theoretically pr…
BaF is one of the potential candidates for the experimental search of the electric dipole moment of the electron (eEDM). The NL-eEDM collaboration is building a new experimental set up to measure the eEDM using the BaF molecule [The NL-eEDM collaboration, Eur. Phys. J. D (2018) 72: 197]. To analyze the results of such an experiment, one would require the accurate value of the molecular ${\mathcal{P,T}}$-odd interaction parameters that cannot be measured from any experiment. In this work, we report the precise value of the ${\mathcal{P,T}}$-odd interaction parameters of the BaF molecule obtaine…
The four-component relativistic Fock space coupled cluster method is used to describe the magnetic hyperfine interaction in low-lying electronic states of the KCs molecule. Both diagonal and off-diagonal matrix elements as functions of the internuclear separation $R$ are calculated within the finite-field scheme. The resulting matrix elements exhibit very weak dependence on $R$ for the separations exceeding 8 Å, whereas in the vicinity of the ground-state equilibrium the deviation of molecular HFS matrix elements from the atomic values reaches 15\%. The dependence of the computed HFS couplings…
The multi-configuration Dirac-Hartree-Fock method was employed to calculate the total and excitation energies, oscillator strengths and hyperfine structure constants for low-lying levels of Sm I. In the first-order perturbation approximation, we systematically analyzed correlation effects from each electrons and electron pairs. It was found that the core correlations are of importance for physical quantities concerned. Based on the analysis, the important configuration state wave functions were selected to constitute atomic state wave functions. By using this computational model, our excitatio…
We have developed an all-particle Fock-space relativistic coupled-cluster method to calculate the properties of two-valence atoms and ions. Using the method we compute the properties associated with hyperfine induced $^1S_0 - ^3P^o_0$ clock transition in Al$^+$. Our result of the $^3P^o_0$ metastable state life time, $20.20 \pm 0.91$ s, is in excellent agreement with the experimental value, $20.60 \pm 1.4$ s [Phys. Rev. Lett. {\bf 98}, 220801 (2007)]. Our studies show that the contributions from the triple excitations, and the corrections from the Breit interaction and QED effects are essentia…
We report the value of the electric quadrupole moment of $^{209}$Bi extracted from the atomic data. For this, we performed electronic structure calculations for the ground $^4S^o_{3/2}$ and excited $^2P^o_{3/2}$ states of atomic Bi using the Dirac-Coulomb-Breit Hamiltonian and the Fock space coupled cluster method with single, double, and full triple amplitudes for the three-particle Fock space sector. The value of the quadrupole moment of $^{209}$Bi, $Q(^{209}$Bi$)=-418(6)$~mb, derived from the resulting electric field gradient values and available atomic hyperfine splittings is in excellent …
Accurate predictions of hyperfine structure (HFS) constants are important in many areas of chemistry and physics, from the determination of nuclear electric and magnetic moments to benchmarking of new theoretical methods. We present a detailed investigation of the performance of the relativistic coupled cluster method for calculating HFS constants withing the finite-field scheme. The two selected test systems are $^{133}$Cs and $^{137}$BaF. Special attention has been paid to construct a theoretical uncertainty estimate based on investigations on basis set, electron correlation and relativistic…
The relativistic multiconfiguration Dirac-Hartree-Fock (MCDHF) and the non-relativistic multiconfiguration Hartree-Fock (MCHF) methods have been employed to calculate the magnetic dipole and electric quadrupole hyperfine structure constants of zinc. The calculated electric field gradients for the $ 4s 4p \,\, ^3 \! P^o_{1} $ and $ 4s 4p \,\, ^3 \! P^o_{2} $ states, together with experimental values of the electric quadrupole hyperfine structure constants, made it possible to extract a nuclear electric quadrupole moment $ Q(^{67}{\rm Zn}) = 0.122(10) $ b. The error bar has been evaluated in a q…
Multiconfiguration Hartree-Fock (MCHF) and multiconfiguration Dirac-Hartree-Fock (MCDHF) calculations are performed for the $2p^{5}~^{2}P^{o}$, $2p^4(^{3}P)3s~^{4}P$, $2p^4(^{3}P)3s~^{2}P$ and $2p^4(^{3}P)3p~^{4}S^o$ states of $^{19}$F~I to determine their hyperfine constants. Several computing strategies are considered to investigate electron correlation and relativistic effects. High-order correlation contributions are included in MCHF calculations based on single and double multireference (SD-MR) expansions. The largest components of the single reference MCHF wave functions are selected to …
Large-scale $\textit{ab initio}$ calculations of the electric field gradient, which constitutes the electronic contribution to the electric quadrupole hyperfine constant $B$, were performed for the $5s^25p6s$ $^{1,3}\!P^{\rm o}_1$ excited states of tin, using three independent computational strategies of the variational multiconfiguration Dirac-Hartree-Fock method and a fourth approach based on the configuration interaction Dirac-Fock-Sturm theory. For the $5s^25p6s$ $^{1}\!P^{\rm o}_1$ state, the final value of $B/Q =703(50)$ MHz/b differs by $0.4\%$ from the one recently used by Yordanov ${\…
Radiative and interelectronic-interaction corrections to the hyperfine splitting in highly charged B-like ions
The ground-state hyperfine splitting values of high-Z boronlike ions are calculated. Calculation of the interelectronic-interaction contribution is based on a combination of the 1/Z perturbation theory and the large-scale configuration-interaction Dirac-Fock-Sturm method. The screened QED corrections are evaluated utilizing an effective screening potential approach. Total hyperfine splitting energies are presented for several B-like ions of particular interest: {}^{45}Sc{}^{16+}, {}^{57}Fe{}^{21+}, {}^{207}Pb{}^{77+}, and {}^{209}Bi{}^{78+}. For lead and bismuth the experimental values of the …
In the weak-magnetic-field approximation, we derived a general expression of hyperfine-induced Landé $g$-factors. By using this formula and the multi-configuration Dirac-Hartree-Fock theory, the $g$-factors were calculated for the $3s3p~^3\!P^o_0$ clock state in $^{27}$Al$^+$ and $5s5p~^3\!P^o_0$ in $^{87}$Sr. The present results, $δg^{(1)}_{\rm hfs}(^3\!P^o_0) = -1.183(6) \times 10^{-3}$ for $^{27}$Al$^+$ and $δg^{(1)}_{\rm hfs}(^3\!P^o_0) = 7.78(30) \times 10^{-5}$ for $^{87}$Sr agree with experimental values very well. Our theory is also useful to predict hyperfine-induced Landé $g$-factors…
The hyperfine splitting of the ground state of selected B-like ions within the range of nuclear charge numbers $Z=49-83$ is investigated in detail. The rigorous QED approach together with the large-scale configuration-interaction Dirac-Fock-Sturm method are employed for the evaluation of the interelectronic-interaction contributions of first and higher orders in $1/Z$. The screened QED corrections are evaluated to all orders in $αZ$ by using an effective potential. The influence of nuclear magnetization distribution is taken into account within the single-particle nuclear model.
A theoretical study of the C- 4So_3/2 and 2Do_{3/2,5/2} bound states and C ground configuration: fine and hyperfine structures, isotope shifts and transition probabilities
本工作是对C-的2 p 3 4SO 3/2和2 Do_{3/2,5/2}态以及中性碳的2 p 2 3 P_{0,1,2}，1 D_2和1 S_0态的从头算研究。我们使用多组态Hartree-Fock方法，专注于波函数本身的准确性。我们获得了所有的C-脱离阈值，包括约0.5%的相关效应。计算了同位素位移和超精细结构。后者实现的精度为0.1 MHz的顺序。还估计了配置内转移概率。
In previous work devoted to {\it ab initio} calculations of hyperfine structure constants in nitrogen and fluorine atoms, we observed sizeable relativistic effects, a priori unexpected for such light systems, that can even largely dominate over electron correlation. We observed that the atomic wave functions calculated in the Breit-Pauli approximation describe adequately the relevant atomic levels and hyperfine structures, even in cases for which a small relativistic $LS$-term mixing becomes crucial. In the present work we identify new levels belonging to the spectroscopic terms $2p^4(^3\!P) 3…
Relativistic many-body calculations of energy levels, hyperfine constants, electric-dipole matrix elements and static polarizabilities for alkali-metal atoms
The Dirac-Hartree-Fock plus many-body perturbation theory (DHF+MBPT) method has been used to calculate hyperfine structure constants for Fr. Calculated hyperfine structure anomaly for hydrogen-like ion has been shown to be in good agreement with analytical expressions. It has been shown that the ratio of the anomalies for $s$ and $p_{1/2}$ states is weakly dependent on the principal quantum number. Finally, we estimate Bohr--Weisskopf corrections for several Fr isotopes. Our results may be used to improve experimental accuracy for the nuclear $g$ factors of short-lived isotopes.
Atomic data benchmarked by Large-scale Multiconfiguration Dirac-Hartree-Fock Calculations for Beryllium
Fudan University（复旦大学）；Anhui Normal University（安徽师范大学）；Malmö University（马尔默大学）；Vilnius University（维尔纽斯大学）；Université libre de Bruxelles（布鲁塞尔自由大学）；Uppsala University（乌普萨拉大学）
Roles of electron correlation effects in the determination of attachment energies, magnetic dipole hyperfine structure constants and electric dipole (E1) matrix elements of the low-lying states in the singly charged cadmium ion (Cd$^+$) have been analyzed. We employ the singles and doubles approximated relativistic coupled-cluster (RCC) method to calculate these properties. Intermediate results from the Dirac-Hartree-Fock approximation, second-order many-body perturbation theory and considering only the linear terms of the RCC method are given to demonstrate propagation of electron correlation…
We demonstrate the importance of electron correlation effects in the hyperfine structure constants of many low-lying states in $^{210}$Fr and $^{212}$Fr. This is achieved by calculating the magnetic dipole and electric quadrupole hyperfine structure constants using the Dirac-Fock approximation, second order many-body perturbation theory and the coupled-cluster method in the singles and doubles approximation in the relativistic framework. By combining our recommended theoretical results with the corresponding experimental values, improved nuclear magnetic dipole and electric quadrupole moments …
Fock-space perturbed relativistic coupled-cluster calculations of electric dipole polarizability and nuclear spin-dependent parity non-conservation in Cs
Employing two state-of-the-art methods, multiconfiguration Dirac--Hartree--Fock and second-order many-body perturbation theory, highly accurate calculations are performed for the lowest 272 fine-structure levels arising from the $2s^{2} 2p^{3}$, $2s 2p^{4}$, $2p^{5}$, $2s^{2} 2p^{2} 3l$~($l=s,p,d$), $2s 2p^{3}3l$ ($l=s,p,d$), and $2p^{4} 3l$ ($l=s,p,d$) configurations in nitrogen-like Ge XXVI. Complete and consistent atomic data, including excitation energies, lifetimes, wavelengths, hyperfine structures, Landé $g_{J}$-factors, and E1, E2, M1, M2 line strengths, oscillator strengths, and trans…
Collisions of metastable antiprotonic helium atoms with atoms of the medium induce, among other processes, transitions between hyperfine structure (HFS) states, as well as shifts and broadening of microwave M1 spectral lines. In order to obtain matrix potential of interaction between $(\mathrm{\bar{p} He} ^+)$ and $\mathrm{He}$, we have calculated the potential energy surface (PES) in the framework of unrestricted Hartree-Fock method taking into account electron correlations in the second-order perturbation theory (MP2). With this potential, the system of close-coupling equations for HFS chann…
The microwave clock frequency of the $|5s~^2S_{1/2}, F=0,m_F=0 \rangle \leftrightarrow |5s~^2S_{1/2}, F=1,m_F=0 \rangle$ transition in the $^{113}$Cd$^+$ ion has been reported as 15199862855.0192(10) Hz [Opt. Lett. {\bf 40}, 4249 (2015)]. Fractional systematic due to the black-body radiation (BBR) shift ($β$) arising from the Stark effect in the above clock transition was used as $-1.1 \times 10^{-16}$ from our unpublished preliminary estimation. We present here a precise value as $β=-1.815(77) \times 10^{-16}$ by carrying out rigorous calculations of third-order polarizabilities of the hyperf…
Large scale ab initio calculations of the electric contribution (i.e. the electric field gradient) to the electric quadrupole hyperfine interaction constants $B$ for the $5p~^2P_{3/2}$ state in $^{109}$Cd$^+$ ion and the $5s5p~^3P_{1,2}$ states in neutral $^{109}$Cd atom were performed. To probe the sensitivity of $B$ to different electron correlation effects, six sets of variational multi-configuration Dirac-Hartree-Fock and relativistic configuration interaction calculations employing different strategies were carried out. The calculated electric field gradients, together with experimental v…
Energy levels of 30 low-lying states of Lu2+ and allowed electric-dipole matrix elements between these states are evaluated using a relativistic all-order method in which all single, double and partial triple excitations of Dirac-Fock wave functions are included to all orders of perturbation theory. Matrix elements are critically evaluated for their accuracy and recommended values of the matrix elements are given together with uncertainty estimates. Line strengths, transition rates and lifetimes of the metastable 5d(3/2) and 5d(5/2) states are calculated. Recommended values are given for stati…
Neutral uranium (U I) is a very difficult atom for theoretical calculations due to a large number of valence electrons, six, strong valence-valence and valence-core correlations, high density of states, and relativistic effects. Configuration-interaction many-body perturbation theory (CI-MBPT) can treat efficiently valence-core correlations and relativistic effects, but because the formalism was developed for Dirac-Hartree-Fock (DHF) starting potential that does not contain valence electrons, quite large CI space is needed to compensate for +6 charge of such a potential. Much more efficient is…
The hyperfine interaction as a probe of the microscopic structure of the atomic nucleus
Center for Quantum Nanoscience, Institute for Basic Science（量子纳米科学中心，基础科学研究院）；Université de Strasbourg, CNRS, Institut de Physique et Chimie des Matériaux de Strasbourg（斯特拉斯堡大学，法国国家科学研究中心，斯特拉斯堡材料物理与化学研究所）；Ewha Womans University（梨花女子大学）；Université de Strasbourg, CNRS, Institut de Chimie（斯特拉斯堡大学，法国国家科学研究中心，化学研究所）；Université de Strasbourg, CNRS, Institut pluridisciplinaire Hubert Curien（斯特拉斯堡大学，法国国家科学研究中心，于贝尔·居里跨学科研究所）
Relativistic multiconfiguration Dirac-Hartree-Fock (MCDHF) calculations with configuration interaction (CI) are carried out for the $^{1}S_{0}$ and $^{3}P_{0,1}^o$ states in neutral ytterbium by use of the available GRASP2018 package. From the resultant atomic state functions and the RIS4 extension, we evaluate the mass and field shift parameters for the $^{1}S_{0}-\,^{3}P_{0}^o$ (clock) and $^{1}S_{0}-\,^{3}P_{1}^o$ (intercombination) lines. We present improved estimates of the nuclear charge parameters, $λ^{A,A'}$, and differences in mean-square charge radii, $δ\langle r^2\rangle^{A,A'}$, an…
We calculated the magnetic dipole and the electric quadrupole hyperfine interaction constants of 3s3p $^{3,1}P^o_1$ states and the isotope shift, including mass and field shift, factors for transitions from these two states to the ground state 3s$^2~^1S_0$ in Al$^+$ ions using the multiconfiguration Dirac-Hartree-Fock method. The effects of the electron correlations and the Breit interaction on these physical quantities were investigated in detail based on the active space approach. It is found that the CC and the higher-order correlations are considerable for evaluating the uncertainties of t…
{\it Ab initio} studies of electron correlation and Gaunt interaction effects in boron isoelectronic sequence using coupled-cluster theory
本文利用相对论耦合团簇（RCC）方法研究了硼原子等电子序列中2 p $^2P_{1/2}$和2 p $^2P_{3/2}$态的电离势（IPs）和超精细常数A的电子关联和Gaunt相互作用效应，以及它们之间的精细结构分裂（FSS）。原子序数Z的取值范围为8 ~ 21。Gaunt的贡献在Dirac-Fock（DF）和耦合簇（CC）水平的计算。将Gaunt修正后的关联结果与NIST的结果进行了比较。研究了超精细常数A的重要关联贡献，如芯关联、芯极化、对关联等。在这些研究中观察到许多明显的关联效应和相对论效应。据我们所知，在Gaunt极限内，大多数超精细常数在文献中是第一次提出。
Comprehensive calculations of energy levels, radiative transition parameters, hyperfine structure constants A$_J$-B$_J$, Landé g$_J$ factors and isotope shifts for Sc XX
Applications of quantum annealing to magnetic dipole hyperfine structure constants: First results beyond energies for atoms
TCG Centres for Research and Education in Science and Technology（科学技术研究与教育中心）；Indian Institute of Technology Tirupati（蒂鲁帕蒂印度理工学院）；Malmö University（马尔默大学）
