Relativistic Configuration-Interaction and Perturbation Theory Calculations for Heavy Atoms

Heavy atoms present challenges to atomic theory calculations due to the large number of electrons and their complicated interactions. Conventional approaches such as calculations based on Cowan’s code are limited and require a large number of parameters for energy agreement. One promising approach is relativistic configuration-interaction and many-body perturbation theory (CI-MBPT) methods. We present CI-MBPT results for various atomic systems where this approach can lead to reasonable agreement: La I, La II, Th I, Th II, U I, Pu II. Among atomic properties, energies, g-factors, electric dipole moments, lifetimes, hyperfine structure constants, and isotopic shifts are discussed. While in La I and La II accuracy for transitions is better than that obtained with other methods, more work is needed for actinides.

Inclusion of a suite of weathering tracers in the cGENIE Earth system model – muffin release v.0.9.23

The metals strontium (Sr), lithium (Li), osmium (Os) and calcium (Ca), together with their isotopes, are important tracers of weathering and volcanism – primary processes which shape the long-term cycling of carbon and other biogeochemically important elements at the Earth's surface. Traditionally, because of their long residence times in the ocean, isotopic shifts in these four elements observed in the geologic record are almost exclusively interpreted with the aid of isotope-mixing, tracer-specific box models. However, such models may lack a mechanistic description of the links between the cycling of the four metals to other geochemically relevant elements, particularly carbon, or climate. Here we develop and evaluate an implementation of Sr, Li, Os and Ca isotope cycling in the Earth system model cGENIE. The model offers the possibility to study the dynamics of these metal systems alongside other more standard biogeochemical cycles, as well as their relationship with changing climate. We provide examples of how to apply this new model capability to investigate Sr, Li, Os and Ca isotope dynamics and responses to environmental change, for which we take the example of massive carbon release to the atmosphere.

Influence of isotopic composition of silicon on local vibrational modes of vacancy-oxygen complex

Isotopic composition of natural silicon (28Si (92.23 %), 29Si (4.68 %) and 30Si (3.09 %)) affects noticeably the shape of infrared absorption bands related to the oxygen impurity atoms. The positions of local vibrational modes (LVMs), related to quasimolecules 28Si – 16OS – 29Si and 28Si – 16OS – 30Si (OS – substitutional oxygen atom) have been determined for the absorption spectra measured at Т ≅ 20 K and at room temperature (Т ≅ 300 K). An estimation of the isotopic shifts of corresponding modes in a semi empirical way has been done by the fitting the shape of the experimentally measured absorption band related to the vacancy-oxygen center in irradiated Si crystals. The LVM isotope shifts at Т ≅ 300 K are found to be (2.22 ± 0.25) сm–1 for 28Si – 16OS – 29Si and (4.19 ± 0.80) сm–1 for 28Si – 16OS – 30Si in relation to the most intense band with its maximum at (830.29 ± 0.09) cm–1 due to the vibrations of 28Si – 16OS – 28Si, and the full width at half maximum of the A-center absorption bands is (5.30 ± 0.26) cm–1. At Т ≅ 20 K the corresponding values have been determined as (1.51 ± 0.13); (2.92 ± 0.20); (835.78 ± 0.01) and (2.34 ± 0.03) сm–1. A model for the calculation of isotopic shifts in the considered case has been discussed. From an analysis of the observed isotopic shifts some information about the structure of the vacancy-oxygen complex in silicon at Т ≅ 20 K and at room temperature has been obtained.

Inclusion of a suite of weathering tracers in the cGENIE Earth System Model – muffin release v.0.9.10

The metals strontium (Sr), lithium (Li), osmium (Os) and calcium (Ca) and their isotopes are important tracers in the study of changes in weathering rates and volcanism, two main processes which shape the long-term cycling of carbon and other biogeochemically important elements at the Earth's surface. Traditionally, isotopic shifts of these four elements in the geologic record are interpreted with isotope-mixing, tracer-specific box models because of their long residence times in the ocean. However, these models often lack mechanistic links between the cycling of the four metals and other geochemically relevant elements, particularly carbon. Here we develop and evaluate the implementation of Sr, Li, Os and Ca isotopes into the Earth system model cGENIE. The model has the potential to study these metal systems at equilibrium and under perturbations alongside other biogeochemical cycles. We provide examples of how to apply this new model to investigate Sr, Li, Os and Ca isotope dynamics and responses to environmental change.

The Structure of the “Vibration Hole” around an Isotopic Substitution—Implications for the Calculation of Nuclear Magnetic Resonance (NMR) Isotopic Shifts

Calculations of nuclear magnetic resonance (NMR) isotopic shifts often rest on the unverified assumption that the “vibration hole”, that is, the change of the vibration motif upon an isotopic substitution, is strongly localized around the substitution site. Using our recently developed difference-dedicated (DD) second-order vibrational perturbation theory (VPT2) method, we test this assumption for a variety of molecules. The vibration hole turns out to be well localized in many cases but not in the interesting case where the H/D substitution site is involved in an intra-molecular hydrogen bond. For a series of salicylaldehyde derivatives recently studied by Hansen and co-workers (Molecules 2019, 24, 4533), the vibrational hole was found to stretch over the whole hydrogen-bond moiety, including the bonds to the neighbouring C atoms, and to be sensitive to substituent effects. We discuss consequences of this finding for the accurate calculation of NMR isotopic shifts and point out directions for the further improvement of our DD-VPT2 method.