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Mariusz Puchalski

Publications and source records attributed to Mariusz Puchalski.

At least 19 recordsLinked to original sources

Relativistic treatment of diamagnetic susceptibility of helium

We report theoretical calculations of the diamagnetic susceptibility, $χ_0$, of helium atom. We determined the complete relativistic correction to $χ_0$ of the order of $α^4$, where $α$ is the fine structure constant, by including all $α^4$ terms originating from the Dirac and Breit equations for a helium atom in a static magnetic field. Finite nuclear mass corrections to $χ_0$ was also evaluated. To obtain very accurate results and reliable uncertainty estimates we used a sequence of explicitly correlated basis sets of fully optimized Slater geminals. We found that $χ_0=-2.119\,106(34)\cdot10^{-5}$ $a_0^3$ and $χ_0=-2.119\,400(34)\cdot10^{-5}$ $a_0^3$ for $^4$He and $^3$He isotopes, respectively, where $a_0$ is the Bohr radius and the uncertainties shown in the parentheses are due entirely to the very conservative estimate of the neglected QED corrections of the order of $α^5$. Our results are compared with the available experimental data and with previous, incomplete theoretical determinations of the $α^4$ contributions to the diamagnetic susceptibility of helium.

physics.atom-ph

Leading-order QED effects in the ground electronic state of molecular hydrogen

We perform highly accurate calculations of the leading order QED correction to the ground electronic state of molecular hydrogen. Numerical results are obtained for a grid of the internuclear distances $R=0-10$ au with the relative precision of about $10^{-8}$. The major numerical uncertainty of previous QED results [K. Piszczatowski et al., JCTC $\textbf{5}$, 3039 (2009)] has been eliminated. Nevertheless, the discrepancy with measurements in HD at the level of 1.9 $σ$ persists.

physics.atom-ph

Nuclear magnetic shielding in HD and HT

We perform a calculation of the nuclear magnetic shielding in HD and HT molecules, with complete and perturbative accounts for nuclear masses. From the difference in shielding, we obtain the deuteron and triton magnetic moments in agreement with the CODATA value, with the accuracy limited only by nuclear magnetic resonance measurements. Most importantly, our calculations indicate a potential for improved determination of nuclear magnetic moments.

physics.atom-ph

QED theory of the nuclear magnetic shielding in H and $^3$He

The derivation of leading quantum electrodynamic corrections to the nuclear magnetic shielding in light hydrogen- and helium-like atomic systems is described in detail. The presented theoretical approach applies to any light atomic and molecular systems, enabling the determination of the magnetic moment of light nuclei with much higher precision than known presently.

physics.atom-ph

QED effects on the nuclear magnetic shielding of $^3$He

The leading quantum electrodynamic corrections to the nuclear magnetic shielding in one- and two-electron atomic systems are obtained in a complete form, and the shielding constants of $^1$H, $^3$He$^+$, and $^3$He are calculated to be $17.735\,436(3) \cdot 10^{-6}$, $35.507\,434(9)\cdot 10^{-6}$, and $59.967\,029(23)\cdot 10^{-6}$, respectively. These results are orders of magnitude more accurate than previous ones, and, with the ongoing measurement of the nuclear magnetic moment of $^3$He$^+$ and planned $^3$He$^{2+}$, they open the window for high-precision absolute magnetometry using $^3$He NMR probes. The presented theoretical approach is applicable to all other light atomic and molecular systems, which facilitates the improved determination of magnetic moments of any light nuclei.

physics.atom-ph

Fine and hyperfine splitting of the low-lying states of $^9$Be

We perform accurate calculations of energy levels as well as fine and hyperfine splittings of the lowest $^{1,3}\!P_J$, $^{3}\!S_1$, $^{3}\!P^e_J$, and $^{1,3}\!D_J$ excited states of the $^9$Be atom using explicitly correlated Gaussian functions and report on the breakdown of the standard hyperfine structure theory. Because of the strong hyperfine mixing, which prevents the use of common hyperfine constants, we formulate a description of the fine and hyperfine structure that is valid for an arbitrary coupling strength and may have wide applications in many other atomic systems.

physics.atom-ph

Hyperfine structure of the $2\,^3\!P$ state in $^9$Be and the nuclear quadrupole moment

We have performed accurate calculations of the hyperfine structure of the $2\,^3\!P$ state in the $^9$Be atom with the help of highly optimized, explicitly correlated functions, accounting for the leading finite nuclear mass, radiative, nuclear structure and relativistic effects. By comparison with measurements, we have determined the $^9$Be nuclear quadrupole moment to be $Q_{\rm N} = 0.05350(14)$ barns, which is not only the most accurate result, but also disagrees with previous determinations.

physics.atom-ph

Hyperfine structure of the first rotational level in H$_2$, D$_2$ and HD molecules and the deuteron quadrupole moment

We perform the four-body calculation of the hyperfine structure in the first rotational state $J=1$ of the H$_2$, D$_2$, and HD molecules and determine the accurate value for the deuteron electric quadrupole moment $Q_d = 0.285\,699(15)(18)$ fm$^2$ in significant disagreement with former spectroscopic determinations. Our results for the hyperfine parameters agree very well with the currently most accurate molecular-beam magnetic resonance measurement performed several decades ago by N.F. Ramsey and coworkers. They also indicate the significance of previously neglected nonadiabatic effects. Moreover, a very good agreement with the recent calculation of $Q_d$ based on the chiral effective field theory, although much less accurate, indicates the importance of the spin dependence of nucleon interactions in the accurate description of nuclei.

physics.chem-ph

Second virial coefficients for helium-4 and helium-3 from accurate relativistic interaction potential

The second virial coefficient and the second acoustic virial coefficient for helium-4 and helium-3 are computed for a wide range of temperatures (0.5 - 1000K) using a highly accurate nonrelativistic interaction potential [M. Przybytek et al., Phys. Rev. Lett. 119, 123401 (2017)] and recalculated relativistic and quantum-electrodynamic components. The effects of the long-range retardation and of the nonadiabatic coupling of the nuclear and electronic motion are also taken into account. The results of our calculations represent at least fivefold improvement in accuracy compared to the previous ab initio work. The computed virial coefficients agree well with the most accurate recent measurements but have significantly smaller uncertainty.

physics.chem-ph

QED calculation of the $\bf{2p}$ fine structure in Li-like ions

Large-scale {\em ab initio} QED calculations are performed for the $2p_{3/2}$--$2p_{1/2}$ fine-structure interval of Li-like ions with nuclear charges $Z = 5\,$--$\,92$. Improved theoretical predictions are obtained by combining together two complementary theoretical methods, namely, the approach that accounts for all orders in the binding nuclear strength and the nonrelativistic QED approach that accounts for all orders in the nonrelativistic electron-electron interaction. The resulting unified approach provides theoretical predictions which are more accurate than the available experimental results across the interval of the nuclear charges considered.

physics.atom-ph

QED calculation of ionization energies of $1snd$ states in helium

Quantum electrodynamical (QED) calculations of ionization energies of the $1snd\,D$ states are performed for the helium atom. We reproduce the previously known relativistic and QED effects up to order $mα^5$ and extend the theory by calculating the complete $mα^6$ correction. The total contribution of the $mα^6$ effects is shown to be much smaller than previously estimated, due to a large cancelation between the radiative and non-radiative parts of this correction. As a result of our calculations, we confirm the previously reported deviations between measured transition energies and theoretical predictions for the $nD$--$2S$ and $nD$--$2P$ transitions. Possible reasons for this discrepancy are analyzed.

physics.atom-ph

Hyperfine structure in the HD molecule

We investigate interactions between the proton spin, the deuteron spin, and the orbital angular momentum in the electronic ground state of the HD molecule. These interactions lead to hyperfine splittings of molecular energy levels. Our numerical results for the first rotational level agree well with the currently most accurate measurement performed by Ramsey {\em et al.} in the 1950s. Knowledge of the hyperfine structure of other levels is necessary for the accurate determination of rovibrational transition energies in spectroscopic measurements. We present theoretical predictions and share the numerical code used to perform numerical calculations. This work sets the ground for high precision spectroscopic tests of hyperfine interactions in molecular systems. In particular we determine the value of the deuteron quadrupole moment $Q = 0.2856(2)$ fm$^2$ and give outlook for improving its accuracy by three orders of magnitude.

physics.chem-ph

QED calculation of the dipole polarizability of helium atom

The QED contribution to the dipole polarizability of the $^4$He atom was computed, including the effect of finite nuclear mass. The computationally most challenging contribution of the second electric-field derivative of the Bethe logarithm was obtained using two different methods: the integral representation method of Schwartz and the sum-over-states approach of Goldman and Drake. The results of both calculations are consistent, although the former method turned out to be much more accurate. The obtained value of the electric-field derivative of the Bethe logarithm, equal to $0.048\,557\,2(14)$ in atomic units, confirms the small magnitude of this quantity found in the only previous calculation [G. Łach, B. Jeziorski, and K. Szalewicz, Phys. Rev. Lett. 92, 233001 (2004)], but differs from it by about 5\%. The origin of this difference is explained. The total QED correction of the order of α 3 in the fine-structure constant α amounts to 30.6671(1)$\cdot 10^{-6}$, including the 0.1822$\cdot 10^{-6}$ contribution from the electric-field derivative of the Bethe logarithm and the 0.01112(1)$\cdot 10^{-6}$ correction for the finite nuclear mass, with all values in atomic units. The resulting theoretical value of the molar polarizability of helium-4 is $0.517\,254\,08(5)\,$cm$^3$/mol with the error estimate dominated by the uncertainty of the QED corrections of order $α^4$ and higher. Our value is in agreement with but an order of magnitude more accurate than the result $0.517\, 254\, 4(10)\,$cm$^3$/mol of the most recent experimental determination [C. Gaiser and B. Fellmuth, Phys. Rev. Lett. 120, 123203 (2018)].

physics.atom-ph

Rovibrational energy levels of the hydrogen molecule through nonadiabatic perturbation theory

We present an accurate theoretical determination of rovibrational energy levels of the hydrogen molecule and its isotopologues in its electronic ground state. We consider all significant corrections to the Born-Oppenheimer approximation, obtained within nonadiabatic perturbation theory, including the mixed nonadiabatic-relativistic effects. Quantum electrodynamic corrections in the leading $α^5\,m$ and the next-to-leading $α^6\,m$ orders, as well as finite nuclear size effect, are also taken into account but within the Born-Oppenheimer approximation only. Final results for the transition wavelength between rovibrational levels achieve accuracy of the order of $10^{-3}$--$10^{-7}$ cm$^{-1}$, and are provided by simple to use computer code.

physics.chem-ph

Dissociation Energy of Molecular Hydrogen Isotopologues

The nonrelativistic energy together with relativistic and quantum electrodynamic corrections for all the molecular hydrogen isotopologues (D$_2$, T$_2$, HD, HT, DT) were evaluated without expansion in the electron-nucleus mass ratio. The obtained results significantly improve the uncertainty of theoretical predictions, reaching a value below 1 MHz for the total dissociation energy. We observe good agreement with the experimental value for D$_2$ and $3\,σ$ discrepancy for the HD molecule, while no experimental values for the dissociation energy of molecules involving tritium have yet been obtained.

physics.chem-ph

Quantum electrodynamic corrections to the $1s3d$ states of the helium atom

We perform quantum electrodynamic calculations of the ionization energy of the $1s3d$ states of the $^4$He atom, including a complete evaluation of the $mα^6$ correction. We find a large contribution from the nonradiative part of this correction, which has not been accounted for in previous investigations. The additional contribution shifts theoretical predictions for ionization energies by about 10$\,σ$. Despite this shift, we confirm the previously reported systematic deviations between measured experimental results and theoretical predictions for transitions involving $3D$ states. The reason for these deviations remains unknown.

physics.atom-ph

Refractive index and generalized polarizability

We investigate the role of retardation corrections to polarizability and to refractive index. We found that the classical electromagnetic theory of dielectrics requires corresponding modifications in terms of nonlocality of the dielectric constant. This nonlocality should be taken into account in the interpretation of accurate measurements of the optical refractivity.

physics.class-ph

Nuclear Charge Radii of $^{10,11}$B

The first determination of the nuclear charge radius by laser spectroscopy for a five-electron system is reported. This is achieved by combining high-accuracy ab initio mass-shift calculations and a high-resolution measurement of the isotope shift in the $2s^2 2p\, ^2\mathrm{P}_{1/2} \rightarrow 2s^2 3s\, ^2\mathrm{S}_{1/2}$ ground state transition in boron atoms. Accuracy is increased by orders of magnitude for the stable isotopes $^{10,11}$B and the results are used to extract their difference in the mean-square charge radius $\langle r^2_\mathrm{c}\rangle^{11} - \langle r^2_\mathrm{c}\rangle^{10} = -0.49\,(12)\,\mathrm{fm}^2$. The result is qualitatively explained by a possible cluster structure of the boron nuclei and quantitatively used as a benchmark for new ab initio nuclear structure calculations using the no-core shell model and Green's function Monte Carlo approaches.

physics.atom-ph