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arXiv:2005.04638 · Physical Chemistry Chemical Physics

Bonding in the helium dimer in strong magnetic fields: the role of spin and angular momentum

Jon Austad, Alex Borgoo, Erik I. Tellgren, Trygve Helgaker

Published Jan 1, 2020• 22 citations
arXivHTMLPDF

Abstract

We investigate the helium dimer in strong magnetic fields, focusing on the spectrum of low-lying electronic states and their dissociation curves, at the full configuration-interaction level of theory. To address the loss of cylindrical symmetry and angular momentum as a good quantum number for nontrivial angles between the bond axis and magnetic field, we introduce the almost quantized angular momentum (AQAM) and show that it provides useful information about states in arbitrary orientations. In general, strong magnetic fields dramatically rearrange the spectrum, with the orbital Zeeman effect bringing down states of higher angular momentum below the states with pure σ character as the field strength increases. In addition, the spin Zeeman effect pushes triplet states below the lowest singlet; in particular, a field of one atomic unit is strong enough to push a quintet state below the triplets. In general, the angle between the bond axis and the magnetic field also continuously modulates the degree of σ, π, and δ character of bonds and the previously identified perpendicular paramagnetic bonding mechanism is found to be common among excited states. Electronic states with preferred skew field orientations are identified and rationalized in terms of permanent and induced electronic currents.

DOI
10.1039/d0cp03259j

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We investigate the helium dimer in strong magnetic fields, focusing on the spectrum of low-lying electronic states and their dissociation curves, at the full configuration-interaction level of theory. To address the loss of cylindrical symmetry and angular momentum as a good quantum number for nontrivial angles between the bond axis and magnetic field, we introduce the almost quantized angular momentum (AQAM) and show that it provides useful information about states in arbitrary orientations. In general, strong magnetic fields dramatically rearrange the spectrum, with the orbital Zeeman effect bringing down states of higher angular momentum below the states with pure σ character as the field strength increases. In addition, the spin Zeeman effect pushes triplet states below the lowest singlet; in particular, a field of one atomic unit is strong enough to push a quintet state below the triplets. In general, the angle between the bond axis and the magnetic field also continuously modulates the degree of σ, π, and δ character of bonds and the previously identified perpendicular paramagnetic bonding mechanism is found to be common among excited states. Electronic states with preferred skew field orientations are identified and rationalized in terms of permanent and induced electronic currents.
Using field ionization combined with the direct detection of excited neutral atoms we measured the distribution of principal quantum number n of excited He Rydberg states after strong-field excitation at laser intensities well in the tunneling regime. Our results confirm theoretical predictions from semiclassical and quantum mechanical calculations and simultaneously underpin the validity of the semiclassical frustrated tunneling ionization model. Moreover, since our experimental detection scheme is spin sensitive in the case of He atoms, we show that strong-field excitation leads to strong population of triplet states. The origin of it lies in the fact that high angular momentum states are accessible in strong-field excitation. Thus, singlet-triplet transitions become possible due to the increased importance of spin-orbit interaction rather than due to direct laser induced spin-flip processes.
A detailed study of the low-lying electronic states 1 Σ, 3 Σ, 3 Π, 3 Δ of the HeH + molecular ion in parallel to a magnetic field configuration (when α-particle and proton are situated on the same magnetic line) is carried out for B = 0 − 4.414 × 10 13 G in the Born–Oppenheimer approximation. The variational method is employed using a physically adequate trial function. It is shown that for the Σ states the parallel configuration is stable with respect to small deviations. The quantum numbers of the ground state depend on the magnetic field strength. The ground state evolves from the spin-singlet 1 Σ state for small magnetic fields B ≲ 0.5 au to the spin-triplet 3 Σ (unbound or weakly bound) state for intermediate fields and to the spin-triplet strongly bound 3 Π state for B ≳ 15 au. When the HeH + molecular ion exists, it is stable with respect to dissociation.
A spectroscopic study of Rydberg states of helium (n = 30 and 45) in magnetic, electric and combined magnetic and electric fields with arbitrary relative orientations of the field vectors is presented. The emphasis is on two special cases where (i) the diamagnetic term is negligible and both paramagnetic Zeeman and Stark effects are linear (n = 30, B ≤ 120 mT and F = 0-78 V cm⁻¹), and (ii) the diamagnetic term is dominant and the Stark effect is linear (n = 45, B = 277 mT and F = 0-8 V cm⁻¹). Both cases correspond to regimes where the interactions induced by the electric and magnetic fields are much weaker than the Coulomb interaction, but much stronger than the spin-orbit interaction. The experimental spectra are compared to spectra calculated by determining the eigenvalues of the Hamiltonian matrix describing helium Rydberg states in the external fields. The spectra and the calculated energy-level diagrams in external fields reveal avoided crossings between levels of different m ₗ values and pronounced m ₁-mixing effects at all angles between the electric- and magnetic-field vectors other than 0. These observations are discussed in the context of the development of a method to generate dense samples of cold atoms and molecules in a magnetic trap following Rydberg-Stark deceleration.
Abstract A spectroscopic study of Rydberg states of helium ( n = 30 and 45) in magnetic, electric and combined magnetic and electric fields with arbitrary relative orientations of the field vectors is presented. The emphasis is on two special cases where (i) the diamagnetic term is negligible and both paramagnetic Zeeman and Stark effects are linear ( n = 30, B ≤ 120 mT and F = 0–78 V cm −1 ), and (ii) the diamagnetic term is dominant and the Stark effect is linear ( n = 45, B = 277 mT and F = 0–8 V cm −1 ). Both cases correspond to regimes where the interactions induced by the electric and magnetic fields are much weaker than the Coulomb interaction, but much stronger than the spin–orbit interaction. The experimental spectra are compared to spectra calculated by determining the eigenvalues of the Hamiltonian matrix describing helium Rydberg states in the external fields. The spectra and the calculated energy-level diagrams in external fields reveal avoided crossings between levels of different m l values and pronounced m l -mixing effects at all angles between the electric- and magnetic-field vectors other than 0. These observations are discussed in the context of the development of a method to generate dense samples of cold atoms and molecules in a magnetic trap following Rydberg–Stark deceleration.
Photoassociation of 5 s n d 1 D 2 − 5 s 2 1 S 0 ultralong-range Rydberg dimers from an ultracold Sr 84 atomic gas in a magnetic field is studied. In the absence of magnetic fields, the electronic wave function is aligned along the rotating molecular axis through electron-atom scattering. With increasing magnetic field strength, the symmetry axis of the electron wave function becomes determined by the applied field. While the ground-state atom has no spin or net charge to interact directly with the magnetic field, the dimer wave function in the limit of strong magnetic field becomes aligned along the applied field. Photoassociation spectra show that with increasing field, an increasing number of rovibrational states are excited, indicating strong coupling between rotational states within the Rydberg dimer.
The Land\'e ggg factor describes the response of an atomic energy level to an external perturbation by a uniform and constant magnetic field. In the case of many-electron systems, the leading term is given by the interaction ${\ensuremath{\mu}}_{B}\phantom{\rule{0.16em}{0ex}}(\stackrel{P\vec}{L}+2\phantom{\rule{0.16em}{0ex}}\stackrel{P\vec}{S})\ifmmode\cdot\else\textperiodcentered\fi{}\stackrel{P\vec}{B}$, where $\stackrel{P\vec}{L}$ and $\stackrel{P\vec}{S}$ are the orbital and spin angular momentum operators, respectively, summed over all electrons. For helium, a long-standing experimental-theoretical discrepancy for PPP states motivates a re-evaluation of the higher order terms which follow from relativistic quantum theory and quantum electrodynamics (QED). The tensor structure of relativistic corrections involves scalar, vector, and symmetric and antisymmetric tensor components. We perform a tensorial reduction of these operators in a Cartesian basis, using an approach which allows us to separate the internal atomic from the external degrees of freedom (magnetic field) right from the start of the calculation. The evaluation proceeds in a Cartesian basis of helium eigenstates, using a weighted sum over the magnetic projections. For the relativistic corrections, this leads to a verification of previous results obtained using the Wigner-Eckhart theorem. The same method, applied to the radiative correction (Bethe logarithm term) leads to a spin-dependent correction, which is different for singlet versus triplet PPP states. Theoretical predictions are given for singlet and triplet 2P2P2P and triplet 3P3P3P states and compared to experimental results where available.