The magnetic isotopic effect for sulfur nuclei

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, p. 1195, May, 1990.     

Interaction potentials of the RG-I anions, neutrals, and cations (RG = He, Ne, Ar)

Interaction potentials of the iodine atom, atomic cation, and anion with light rare-gas atoms from He to Ar are calculated within the unified ab initio approach using the unrestricted coupled-cluster with singles and doubles and perturbative treatment of triples correlation treatment, relativistic small-core pseudopotential, and an extended basis set. Ab initio points are fit to a flexible analytical function. The calculated potentials are compared with available literature data, assessed in the I(-)-and I+-ion mobility calculations and the Ar-I(-)-anion zero electron kinetic-energy spectra simulations, and analyzed using the correlation rules. The results indicate a high precision of the reported potentials.     

Decoupling approximations for quantum vibrational predissociation dynamics: The tests on the low-level golden rule approaches for some rare gas—Cl2, ICl complexes

Vibrational and rotational decoupling approximations are tested in three-dimensional Fermi Golden Rule calculations on energies, lifetimes, and product state distributions of the vibrationally predissociating atom—diatom van der Waals complexes. The validity of approximate separations of diatom vibration, decoupling of stretching and bending intermolecular motions, and rotational infinite order sudden approximation for product scattering is characterized by comparison with the results of accurate calculations on the Ne ··· Cl₂, Ne ··· ICl, and He ··· ICl systems. The most accurate approximate schemes are recommended. © 1996 by John Wiley & Sons, Inc.     

Tunneling spectroscopy of single electron spin

The possibility of detection of the electron spin of a single paramagnetic species (an atom, a radical, or an ion) on the surface was discussed. The analysis was based on spin chemistry laws taking into account the statistics of the spin states of both the tunneling electron and paramagnetic center. The equations for the tunneling current as a function of temperature and magnetic field strength were derived. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1732–1734, September, 1998.     

Spin squeezing and quantum correlations

We discuss the notion of spin squeezing considering two mutually exclusive classes of spin-s states, namely, oriented and non-oriented states. Our analysis shows that the oriented states are not squeezed while non-oriented states exhibit squeezing. We also present a new scheme for construction of spin-s states using 2s spinors oriented along different axes. Taking the case of s=1, we show that the ‘non-oriented’ nature and hence squeezing arise from the intrinsic quantum correlations that exist among the spinors in the coupled state.     

phosphate hydrate complexes of singly and doubly charged magnesium ions: Structure,energies, and spin states

For mixed magnesium phosphate hydrate complexes containing Mg²⁺ and Mg⁺ cations and HPO₄²⁻, HPO₄⁻, and H₂P₂O₇²⁻ anions, theoretical analysis of the electronic structure and energies has been performed at the model level in order to predict the actual role of these systems in various reactions that occur in the catalytic sites of ATP synthesizing enzymes. The calculations (DFT/B3LYP, MP2 with the 6–31G* basis set) of isolated aqua complexes Mg(H₂O) _n ^p (n = 1−6, p = 0, +1, +2) show that their relative stability monotonically increases with increasing n in each series and sharply decreases at a given n in going from the charged systems of Mg²⁺ (4–16 eV) and Mg⁺ (2–7 eV) to the neutral systems of Mg (<2 eV). An even higher stability is predicted for mixed magnesium complexes. The energies of fragmentation of mixed Mg²⁺ complexes into singlet phosphate and Mg²⁺-containing fragments at n = 0–4 are within 6–27 eV, and the energies of fragmentation into the corresponding radical ions are within 3–10 eV; for the Mg⁺ complexes, the fragmentation energies are also high (6–14 eV). The reasons for the enhanced stability of the complexes of both types have been analyzed with allowance for the predicted specific features of the electron density redistribution upon complex formation. Typical changes in the geometry of the P- and Mg-containing fragments caused by formation of mixed complexes have been discussed in the framework of the vibronic model of heteroligand systems. The high stability of all mixed magnesium complexes relative to various fragmentation products presumably rules out any dissociative processes in them in the course of ATP synthesis with the participation of phosphorylating enzymes.     

State-interacting spin-orbit configuration interaction method for <Emphasis Type="Italic">J</Emphasis>-resolved anisotropic static dipole polarizabilities: Application to Al,Ga, In,and Tl atoms

The state-interacting spin-orbit (SO) configuration interaction (CI) method, which uses the non-relativistic CI wave functions as the basis of the total SO Hamiltonian matrix, is combined with the finite-field approach and applied to J-resolved anisotropic static dipole polarizabilities of the third-group atoms from Al to Tl. Comparison with available data reveals excellent performance of the method for atoms up to the fifth period (In), especially if the scalar relativitic and the high-level correlation corrections are included. The method performs worse for 6s ²6p Tl atom, most likely due to growing effect of the second-order SO coupling. Refined values of all the scalar and the tensor ground-state non-relativistic and J-resolved polarizabilities and, whenever possible, excited-state polarizabilities, are recommended based on the calculations performed and thorough analysis of the literature data.