Nuclear effects in atomic transitions

Atomic electrons are sensitive to the properties of the nucleus they are bound to, such as nuclear mass, charge distribution, spin, magnetization distribution, or even excited level scheme. These nuclear parameters are reflected in the atomic transition energies. A very precise determination of atomic spectra may thus reveal information about the nucleus, otherwise hardly accessible via nuclear physics experiments. This work reviews theoretical and experimental aspects of the nuclear effects that can be identified in atomic structure data. An introduction to the theory of isotope shifts and hyperfine splitting of atomic spectra is given, together with an overview of the typical experimental techniques used in high-precision atomic spectroscopy. More exotic effects at the borderline between atomic and nuclear physics, such as parity violation in atomic transitions due to the weak interaction, or nuclear polarization and nuclear excitation by electron capture, are also addressed.Comment: review article, 53 pages, 14 figure

Entrance Channel X-HF (X=Cl, Br, and I) Complexes studied by High-Resolution Infrared Laser Spectroscopy in Helium Nanodroplets

Rotationally resolved infrared spectra are reported for halogen atom - HF free radical complexes formed in helium nanodroplets. An effusive pyrolysis source is used to dope helium droplets with Cl, Br and I atoms, formed by thermal dissociation of Cl$_2$, Br$_2$ and I$_2$. A single hydrogen fluoride molecule is then added to the droplets, resulting in the formation of the X-HF complexes of interest. Analysis of the resulting spectra confirms that the observed species have $^2\Pi_{3/2}$ ground electronic states, consistent with the linear hydrogen bound structures predicted from theory. Stark spectra are also reported for these species, from which the permanent electric dipole moments are determined.Comment: 41 pages, 16 figures, 5 table

Semiclassical evaluation of kinetic isotope effects in 13-atomic system

The semiclassical instanton approach discussed by Kryvohuz [J. Chem. Phys. 134, 114103 (2011)10.1063/1.3565425] is applied to calculate kinetic H/D isotope effect (KIE) of intramolecular hydrogen transfer in cis-1,3-pentadiene. All 33 vibrational degrees of freedom are treated quantum mechanically with semiclassical approximation. Nuclear quantum effects such as tunneling under the barrier and zero-point energy are automatically incorporated in the theory, and are shown to be responsible for the observed appreciable kinetic isotope effect in cis-1,3-pentadiene. Over the barrier passage is also automatically included. Numerical calculations are performed on an empirical valence bond potential energy surface and compared with the previous experimental and theoretical studies. An estimation of heavy-atom ^(12)C/^(13)C KIE in the same system is also provided and the factors contributing to it are discussed

Isotope shifts of 6s5d 3^3D-states in neutral Barium

Laser spectroscopy of the low lying $^1$P and $^3$D states in atomic barium has been performed. This work contributes substantially to the development of an effective laser cooling and trapping for heavy alkaline earth elements and aims in particular for a better understanding of the atomic wave function of these systems. Isotope shifts and hyperfine structures are ideal probes for the wave functions at the position of the nucleus. This is essential input for a theoretical evaluation of the sensitivity to fundamental symmetry breaking properties like permanent electric dipole moments. We report the first isotope shift measurements of the $^3$D$_{1,2}$-$^1$P$_1$ transitions. A deviation of the King plot from its expected behavior has been observed. Further we have optically resolved the hyperfine structure of the $^3$D$_{1,2}$ states.Comment: 7 pages, 7 figure

Influence of Dielectric Environment upon Isotope Effects onGlycoside Heterolysis: Computational Evaluation and AtomicHessian Analysis

Isotope effects depend upon the polarity of the bulk medium in which a chemical process occurs. Implicit solvent calculations with molecule-shaped cavities show that the equilibrium isotope effect (EIE) for heterolysis of the glycosidic bonds in 5′-methylthioadenosine and in 2-(p-nitrophenoxy)tetrahydropyran, both in water, are very sensitive in the range 2 ≤ ε ≤ 10 to the relative permittivity of the continuum surrounding the oxacarbenium ion. However, different implementations of nominally the same PCM method can lead to opposite trends being predicted for the same molecule. Computational modeling of the influence of the inhomogeneous effective dielectric surrounding a substrate within the protein environment of an enzymic reaction requires an explicit treatment. The EIE (KH/KD) for transfer of cyclopentyl, cyclohexyl, tetrahydrofuranyl and tetrahydropyranyl cations from water to cyclohexane is predicted by B3LYP/6-31+G(d) calculations with implicit solvation and confirmed by B3LYP/6-31+G(d)/OPLS-AA calculations with averaging over many explicit solvation configurations. Atomic Hessian analysis, whereby the full Hessian is reduced to the elements belonging to a single atom at the site of isotopic substitution, reveals a remarkable result for both implicit and explicit solvation: the influence of the solvent environment on these EIEs is essentially captured completely by only a 3 × 3 block of the Hessian, although these values must correctly reflect the influence of the whole environment. QM/MM simulation with ensemble averaging has an important role to play in assisting the meaningful interpretation of observed isotope effects for chemical reactions both in solution and catalyzed by enzymes

Correlation between muonic levels and nuclear structure in muonic atoms

A method that deals with the nucleons and the muon unitedly is employed to investigate the muonic lead, with which the correlation between the muon and nucleus can be studied distinctly. A "kink" appears in the muonic isotope shift at a neutron magic number where the nuclear shell structure plays a key role. This behavior may have very important implications for the experimentally probing the shell structure of the nuclei far away from the $\beta$-stable line. We investigate the variations of the nuclear structure due to the interaction with the muon in the muonic atom and find that the nuclear structure remains basically unaltered. Therefore, the muon is a clean and reliable probe for studying the nuclear structure. In addition, a correction that the muon-induced slight change in the proton density distribution in turn shifts the muonic levels is investigated. This correction to muonic level is as important as the Lamb shift and high order vacuum polarization correction, but is larger than anomalous magnetic moment and electron shielding correction.Comment: 2 figure