The Land\'e $g$ 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 $P$ 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 $P$ states. Theoretical predictions are given for singlet and triplet $2P$ and triplet $3P$ states and compared to experimental results where available.
The Land'e g 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 P 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 P states. Theoretical predictions are given for singlet and triplet 2P and triplet 3P states and compared to experimental results where available.
Abstract A theory of the helium atom was developed by Heisenberg, following his famous principle of “resonance.” His work is based upon Schrodinger’s equation, and in order to allow for the spin of the electrons he introduces extra energy terms, expressing the classical energy of two appropriate magnets. It is the perturbation by this spin energy which produces the triplet separations. Heisenberg’s calculation of these separations is open to three criticisms: (1) He assumes that certain simple forms are correct first approximations to the wave-functions; whereas, owing to degeneracy, it is necessary to take linear combinations of these forms. (2) He estimates the mean values of the spin energy by means of a model built up of precessing vectors. (3) He neglects the radius of the inner orbit in comparison with that of the outer orbit, even when the principal quantum number of the latter is only 2; this is the least satisfactory of several necessary simplifications. Schrödinger’s equation is likely to be supplanted as the foundation of wave-mechanics by the equation recently put forward by Dirae. This fits the spin of the electron neatly into the theory of relativity, and produces the doublets of the hydrogen-like atom in a beautiful manner. Dirac’s q-number theory has been translated into wave-mechanics by Darwin. Apart altogether from the above criticisms of Heisenberg, it seemed expedient to proceed to the theory of an atom with two electrons on the basis of the new equation. Calculations which are independent of the spin, such as the approximate energylevels, and the separation between ortho- and para-terms, are the same on either theory, and are not the concern of this paper. We deal here with spin effects, such as the fine structure of the triplets and intercombinations between ortho- and para-states.
We calculate the energy levels of He+ ion placed in a uniform magnetic field directed perpendicular to the direction of its center of mass (CM) velocity vector, correct to relative order . Our calculations are within the frame work of an approximately relativistic theory, correct to relative order , of a two-particle composite system bound by electromagnetic forces, and written in terms of the position, momentum and spin operators of the constituent particles as proposed by Krajcik and Foldy, and also by Close and Osborn. Since the He+ ion has a net electric charge, the total or the CM momentum is not conserved and a neat separation of the CM and the internal motion is not possible. What is new in our approach is that, for the basis states in a first order degenerate perturbation theory to calculate the effects of the external magnetic field, we use the direct product of the coherent state of the Landau Hamiltonian of the He+ ion in a uniform magnetic field and of the simultaneous eigenstate of the internal Hamiltonian h, j2, l2, s2 and jz, where j, l and s are the internal total, orbital and spin angular moments of the He+ ion. The coherent state is an excellent approximation to the expected classical circular motion of the center of mass (CM) of the He+ ion. In addition to the Z2 a2 corrections to the usual nonrelativistic results, including the small corrections due to the nuclear motion, we also obtain corrections which depend on the kinetic energy (ECM ) of the CM circular motion of the He+ ion, in a nontrivial way. Even though these corrections are proportional to , where M is the mass of the He+ ion, and are small for nonrelativistic CM motion, the results should be verifiable in careful experiments. Our results may also have application in astrophysical observations of the spectral lines of He+ ions in magnetized astrophysical objects.
We theoretically investigate long-range interactions between an excited L-state He atom and two identical S-state He atoms for the cases of the three atoms all in spin-singlet states or all in spin-triplet states, denoted by He(${n}_{0}^{\ensuremath{\lambda}}S$)-He(${n}_{0}^{\ensuremath{\lambda}}S$)-He(${n}_{0}^{\ensuremath{'}\ensuremath{\lambda}}L$), with n0 and ${n}_{0}^{\ensuremath{'}}$ principal quantum numbers, $\ensuremath{\lambda}=1$ or 3 the spin multiplicity, and L the orbital angular momentum of a He atom. Using degenerate perturbation theory for the energies up to second-order, we evaluate the coefficients C3 of the first-order dipolar interactions and the coefficients C6 and C8 of the second-order additive and nonadditive interactions. Both the dipolar and dispersion interaction coefficients, for these three-body degenerate systems, show dependences on the geometrical configurations of the three atoms. The nonadditive interactions start to appear in second-order. To demonstrate the results and for applications, the obtained coefficients Cn are evaluated with highly accurate variationally generated nonrelativistic wave functions in Hylleraas coordinates for $\text{He}(1{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(1{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}S)$, $\text{He}(1{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(1{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}P)$, $\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{1}P)$, and $\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{3}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{3}S)\text{\ensuremath{-}}\text{He}(2{\phantom{\rule{0.16em}{0ex}}}^{3}P)$. The calculations are given for three like nuclei for the cases of hypothetical infinite mass He nuclei, and of real finite mass 4He or 3He nuclei. The special cases of the three atoms in equilateral triangle configurations are explored in detail, and for the cases in which one of the atoms is in a P state, we also present results for the atoms in an isosceles right triangle configuration or in an equally spaced collinear configuration. The results can be applied to construct potential energy surfaces for three helium atom systems.
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.
A series of magic wavelengths for the 23S1 → 23PJ (J = 0, 1, 2) transitions in helium is determined with high precision using the relativistic configuration interaction combined with the radiative potential method. The calculation explicitly incorporates relativistic, finite nuclear mass, and quantum electrodynamic corrections through the inclusion of mass shift and radiative potential operators into the Dirac-Coulomb-Breit Hamiltonian. The resulting magic wavelengths lie entirely within the visible spectrum (400-700 nm) and converge to seven significant digits, making them directly accessible for experimental verification. These accurate predictions serve as benchmarks for testing atomic structure theory and support the development of state-insensitive optical trapping schemes in precision spectroscopy.
We developed a series of correlation-consistent, polarized multiple zeta basis sets optimized specifically for the energy of the 2 3S state of helium atom. These basis sets were subsequently augmented with diffuse functions optimized for the van der Waals constants C6 through C14 which determine the asymptotic behavior of the second-order dispersion interaction between 2 3S helium atoms at large interatomic separation R. The resulting bases were applied to compute the Born-Oppenheimer (BO) potential for the lowest 5Sigmag+ state of the helium dimer. The coupled cluster and the full configuration-interaction techniques were employed to account for the electron correlation effects. The cardinal number extrapolation technique was used to obtain the complete-basis-set limit V(R) for the interaction potential and to find its lower VL(R) and upper VU(R) bounds. The resulting potentials were fitted to an analytical function containing accurate van der Waals constants C6 through C12 (including C11). We found that the complete-basis-set BO potential has a well depth De=1048.24+/-0.36 cm-1. The highest rotationless vibrational level is bound by D14=90.2+/-4.7 MHz, much stronger than the previous most accurate estimation of 15.2 MHz. The error bounds for De and D14 were obtained using the VL(R) and VU(R) potentials. The S-wave scattering length computed using the VL(R), V(R), and VU(R) potentials (assuming atomic masses) is aL=7.41 nm, a=7.54 nm, and aU=7.69 nm, respectively. We also computed the adiabatic, relativistic, and quantum electrodynamics (QED) corrections to the BO potential. When these corrections are taken into account the values of D14 and of a (both computed assuming nuclear masses) are 87.4+/-6.7 MHz and 7.64+/-0.20 nm; the error bounds reflect now also the uncertainty of the included adiabatic, relativistic, and QED corrections. The value of the scattering length resulting from our investigation lies outside the error bounds of all experimental determinations based on the properties of Bose-Einstein condensate of spin-polarized helium atoms.