Attenuations and atomic spin precessions of γ-angular correlations for coulomb excited19F nuclei in single-electron ions

Attenuated γ-angular correlations and atomic spin precessions were measured for single-electron fluorine ions recoiling through vacuum in weak transverse magnetic fields The Coulomb excited long-lived¹⁹F(5/2⁺) state at 197 keV was used as probe. The angular correlations observed in the focal coordinate system of the Coulomb excitation process as well as the spin precessions in weak external fields are well explained with simple electron configurations associated with the highly stripped ions.     

Relativistic effects in HgHe and HgXe CCSD(T) ground state potential curves. Low‐density viscosity simulations of Hg:Xe mixture

The comparison of coupled cluster with single and double excitations and with perturbative correction of triple excitations [CCSD(T)] ground state potential curves of mercury with rare gases (RG): HgHe and HgXe, at several levels of theory is presented. The scalar relativistic (REL) effects and spin‐orbit coupling effects in the ground state potential curves of these weakly bounded dimers are considered. The CCSD(T) ground state potential curves at the level of the Dirac‐Coulomb Hamiltonian (DCH) are compared with CCSD(T) curves at the level of 4‐component spin‐free modified DCH, the scalar 2nd order Douglas‐Kroll‐Hess (DKH2) and the nonrelativistic (NR‐LL) (Lévy‐Leblond) Hamiltonian. In addition, London‐Drude formula and SCF interaction energy curves are employed in the analysis of different contributions of REL effects in dissociation energies of HgRG and Hg₂ dimers. Moreover, the large anharmonicity of the HgHe ground state potential curve is highlighted. The computationally less demanding scalar DKH2 Hamiltonian is employed to calculate the HgXe, Hg₂, and Xe₂ all electron CCSD(T) ground state potential curves in highly augmented quadruple zeta basis sets. These potential curves are used to simulate the shear viscosity of mercury, xenon, and mercury‐xenon (Hg:Xe) mixture. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011     

Theory for the optical properties of small Hg n clusters

The static and dynamical polarizabilities of the Hg-dimer are calculated by using a Hubbard Hamiltonian to describe the electronic structure. The Hamiltonian is diagonalized exactly within a subspace of second-quantized electronic states from which only multiply ionized atomic configurations have been excluded. With this approximation we can describe the most important electronic transitions including the effect of charge fluctuations. We analyze the polarizability as a function of the intraatomic Coulomb interaction which represents the repulsion between electrons. We obtain that this interaction results in strong electronic correlations in the excited states and increases the first excitation energy of the dimer by 0.8 eV in comparison to a calculation which neglects correlations, resulting in a better agreement with the experiment.     

Symmetry in the design of NMR multiple-pulse sequences

The symmetry principles of NMR pulse-sequence design are summarized. The discussion is guided by an analogy with tiling schemes in the decorative arts. The symmetry operations for NMR pulse sequences are discussed in terms of excitation field modifiers and temporal modifiers. The quantum operators which describe the effect of these modifiers on the excitation field spin Hamiltonian are provided. The symmetry transformations of spin propagators, and the different types of pulse-sequence elements are discussed. The common types of symmetry expansion are treated using the propagator transformations and the Euler angles for the excitation field propagators. The selection rules associated with symmetrical pulse sequences are discussed using average Hamiltonian theory.     

Instabilities of the symmetry-adapted restricted-hartree–fock ground state in infinite polyenes. I. Singlet instabilities

The singlet instabilities of the RHF ground state in infinite polyenes have been studied in the framework of a semiempirical PPP Hamiltonian, accounting for long-range Coulomb interactions until convergence of the ground-state energy per electron value. The symmetry-adapted RHF solution (SAS ) has been shown to be unstable to the formation of bond-order alternation waves (BAW 's) and charge-density waves (CDW 's). The CDW solutions have been shown to be higher in energy than the corresponding BAW solutions and to represent saddle points of the energy hypersurface, unstable to the formation of BAW 's for physically realistic range of variation of the semiempirical parameters. Analytical formulas for the SAS ground-state energy per electron have been derived in case of a Coulomb law and a Mataga–Nishimoto formula for the two-center Coulomb integrals.     

A model electronic Hamiltonian to study low-lying electronic states of [Fe(bpy)3]2+ in aqueous solution

A simple model electronic Hamiltonian to describe the potential energy surfaces of several low-lying d-d states of the [Fe(bpy)(3)](2+) complex is developed for use in molecular dynamics (MD) simulation studies. On the basis of a method proposed previously for first-row transition metal ions in aqueous solution, the model Hamiltonian is constructed using density functional theory calculations for the lowest singlet and quintet states. MD simulations are then carried out for the two spin states in aqueous solution in order to examine the performance of the model Hamiltonian. The simulation results indicate that the present model electronic Hamiltonian reasonably describes the potential energy surfaces of the two spin states of the aqueous [Fe(bpy)(3)](2+) system, while retaining sufficient simplicity for application in simulation studies on excited state dynamics.     

Effect of the fifth coordination site on the spin states of bis(benzoylacetylacetanato)bispyridinedicopper(II) complex

The spin and charge excitation gap and spin density have been calculated for bis(benzoylacetylacetanato)bispyridinedicopper(II) using a valence bond basis and model Hamiltonian based on the Pariser—Parr—Pople (PPP) approximation. The singlet—triplet energy gap depends upon the exchange interaction (K_oo) of the bridging oxygen atom. The results of this 12-orbital, 18-electron system are compared with those of a 10-orbital, 14-electron system, viz. bis(benzoylacetylacetanato)dicopper(II), the latter without axial ligation. Changing the nitrogen to oxygen in the fifth coordination site does not seem to affect the singlet—triplet energy gap and spin and charge density on the copper(II) atoms. The results indicate that K_oo, which is sensitive to geometry, plays a decisive role in determining the excitation gap.     

High‐spin behavior of molecular crystals and extended π systems

The qualitative rules for the existence of high‐spin ground states in extended systems and molecular crystals are examined here on a firmer theoretical footing. Extended systems have been categorized into three groups, namely, type I, type II, and type III, depending on the type of bonding interactions. The general form of the spin Hamiltonian operators have been written down. The active spaces have been restricted to the minimum size for each of these three types of spin systems. The zeroth‐order state vectors and the Hartree–Fock ground‐state energies have been identified for unit species of each type. The extended system Hamiltonian operators are further truncated in such a way that only the nearest‐neighbor interactions are retained. Expressions have been derived for the energy gap from a molecular orbital approach. The relatively small effects of electron correlation on the energy gaps have been estimated for the type I systems, which belong to the systems of solid‐state physics. In particular, it has been shown that for the type I systems the singlet–triplet gap, and hence the ferromagnetic coupling constant, primarily depends upon the difference of one‐electron kinetic energies and not on the two‐electron exchange integrals. This result agrees with the concept of kinetic exchange that was introduced in the context of a resonating valence‐bond formalism. Type II systems are exemplified by extended systems that can be prepared from conjugated molecules while organic molecular crystals form examples of type III species. For these systems, however, the Coulomb exchange interaction has been shown to dominate the energy gap. A quick review of the Heisenberg spin Hamiltonian for the H₂ molecule is sufficient to point out that the sign of the calculated ferromagnetic coupling constant depends on the method of calculation, the nature of the basis set, and the bond length. This is amply supported by ab initio calculations on this species. Numerical data have also been obtained from computations on m‐phenylene‐coupled nitroxy radicals and stacks of α‐nitronyl nitroxide, but these calculations have been based on a semiempirical quantum chemical methodology (INDO) since some of the species involved are exceedingly large. Computed energy gaps are in good agreement with experimental and other theoretical (AM1, PM3) results. Nevertheless, for the dimer, trimer, tetramer, and pentamer of the type II specimen, the important π orbitals are far from being degenerate. The quantitative results clearly deviate from the criterion of degeneracy that was suggested from qualitative theories for the existence of a high‐spin ground state. Therefore, the criteria for the existence of high spins have been reformulated in terms of the monomer orbitals. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 308–324, 2000     

Linear-scaling formation of Kohn-Sham Hamiltonian: application to the calculation of excitation energies and polarizabilities of large molecular systems

We present calculations of excitation energies and polarizabilities in large molecular systems at the local-density and generalized-gradient approximation levels of density-functional theory (DFT). Our results are obtained using a linear-scaling DFT implementation in the program system DALTON for the formation of the Kohn-Sham Hamiltonian. For the Coulomb contribution, we introduce a modification of the fast multipole method to calculations over Gaussian charge distributions. It affords a simpler implementation than the original continuous fast multipole method by partitioning the electrostatic Coulomb interactions into "classical" and "nonclassical" terms which are explicitly evaluated by linear-scaling multipole techniques and a modified two-electron integral code, respectively. As an illustration of the code, we have studied the singlet and triplet excitation energies as well as the static and dynamic polarizabilities of polyethylenes, polyenes, polyynes, and graphite sheets with an emphasis on the trends observed with system size.     

Dissipative quantum dynamics with the surrogate Hamiltonian approach. A comparison between spin and harmonic baths

The dissipative quantum dynamics of an anharmonic oscillator coupled to a bath is studied with the purpose of elucidating the differences between the relaxation to a spin bath and to a harmonic bath. Converged results are obtained for the spin bath by the surrogate Hamiltonian approach. This method is based on constructing a system-bath Hamiltonian, with a finite but large number of spin bath modes, that mimics exactly a bath with an infinite number of modes for a finite time interval. Convergence with respect to the number of simultaneous excitations of bath modes can be checked. The results are compared to calculations that include a finite number of harmonic modes carried out by using the multiconfiguration time-dependent Hartree method of Nest and Meyer [J. Chem. Phys. 119, 24 (2003)]. In the weak coupling regime, at zero temperature and for small excitations of the primary system, both methods converge to the Markovian limit. When initially the primary system is significantly excited, the spin bath can saturate restricting the energy acceptance. An interaction term between bath modes that spreads the excitation eliminates the saturation. The loss of phase between two cat states has been analyzed and the results for the spin and harmonic baths are almost identical. For stronger couplings, the dynamics induced by the two types of baths deviate. The accumulation and degree of entanglement between the bath modes have been characterized. Only in the spin bath the dynamics generate entanglement between the bath modes.     

A sum rule approach to collective spin modes in paramagnetic clusters,cavities and shells

We study spin collective modes in paramagnetic systems using a sum rule approach. We give a simple and analytical expression for the static magnetic polarizability of finite size systems in terms of their radii and of the magnetic susceptibility of a uniform system. A systematics for the mean excitation energy of spin modes in clusters and shells is given. In metal spheres, the hydrodynamical model is solved and compared with the sum rule approach. An estimate for the mean excitation energy of the spin dipole collective state in fullerene is given.     

Single nucleon transfer reactions near Coulomb barrier on <Superscript>197</Superscript>Au

Summary Single neutron transfer reactions on ¹⁹⁷Au induced by ¹²C and ¹⁶O at near Coulomb barrier energies have been studied using radiochemical and off-line gamma-ray spectrometric techniques. High spin yield fraction (HSF = σ_m/(σ_m+σ_g)) for ^196m,gAu and formation cross section ratio (σ₁₉₈/σ₁₉₆) of ¹⁹⁸Au and ¹⁹⁶Au have been determined for both ¹⁹⁷Au+¹²C and ¹⁹⁷Au+¹⁶O reactions at different excitation energies near the Coulomb barrier. The HSF of ^196m,gAu and σ₁₉₈/σ₁₉₆ values in both reactions are seen to sharply increase with increasing excitation energy near the Coulomb barrier and then slowly increase reaching a constant value at high projectile energy. These observations have been analyzed in terms of nuclear structural and kinematic parameters. A comparison the effects of Coulomb excitation and nucleon transfer process during heavy-ion interactions indicates a predominant effect of the latter process in the background of the Coulomb excitation. Observed reaction systematics seem to follow the quasi-elastic transfer process.     

Calculation of the electronic properties of metal dimers

The low-energy excitation spectra of metal dimers are determined by solving exactly a realistic many-body Hamiltonian with inter- and intra-atomic Coulomb interactions. Our results for Cu₂ and Ag₂ are in very good agreement with the excitation energies derived from recent photodetachment experiments. The characteristics of the many-body excited states in these clusters are briefly discussed.     

Hamiltonian for the spin quantum Hall effect solution and derivation based on an SU (2) gauge field

A Hamiltonian to describe a spin quantum Hall effect with two types of spin‐orbit coupling is introduced and the eigenfunctions and eigenvalues are obtained for it. It is shown that this Hamiltonian also results by gauging a kinetic energy Hamiltonian by an SU (2) gauge field. The Berry phase is obtained from the model wavefunction for the model and used to define a filling factor. This allows for the calculation of the spin Hall conductivity. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Anomalous Light‐Induced Spin‐State Switching for Iron(II) Spin‐Crossover Molecules in Direct Contact with Metal Surfaces

Light‐induced spin‐state switching is one of the most attractive properties of spin‐crossover materials. In bulk, low‐spin (LS) to high‐spin (HS) conversion via the light‐induced excited spin‐state trapping (LIESST) effect may be achieved with a visible light, while the HS‐to‐LS one (reverse‐LIESST) requires an excitation in the near‐infrared range. Now, it is shown that those phenomena are strongly modified at the interface with a metal. Indeed, an anomalous spin conversion is presented from HS state to LS state under blue light illumination for Fe^II spin‐crossover molecules that are in direct contact with metallic (111) single‐crystal surfaces (copper, silver, and gold). To interpret this anomalous spin‐state switching, a new mechanism is proposed for the spin conversion based on the light absorption by the substrate that can generate low energy valence photoelectrons promoting molecular vibrational excitations and subsequent spin‐state switching at the molecule–metal interface.     

Calculation of molecular systems via coordinate wave functions

Expressions are derived for the matrix elements of the Coulomb interaction of a system of charges consisting of two subsystems, each in a state with a given spin. It is found that the interaction energy of the two subsystems is independent of the spin S₂ of the second subsystem to quantities of the order of the square of the overlap integral for the one-electron orbitals if the first subsystem has spin S[₁=0. Examples are given of calculations by this method. An appendix gives tables of the matrices needed to calculate the interaction energy of two subsystems with a total number of particles from 3 to 6.     

A contribution to the theory of multiple-pulse narrowing of NQR lines

A theory of the high resolution NQR spectroscopy experiments is developed in the framework of an average Hamiltonian approach analogous to that used in the theory of the NMR line pulse narrowing in solids. A specially constructed unitary operator is found making it possible to treat r. f. excitation of spin systems with nonequidistant spectra, spin and EFG asymmetry parameter being arbitrary. Time averaging is used to get an average Hamiltonian appropriate to dealing with arbitrary periodic multiple-pulse sequences. Relations between the sequence parameters are found ensuring realization of the averaging above mentioned in different cases of interest. The theoretical results obtained are consistent with available data on NQR multiple-pulse experiments.     

Relativistic theory for indirect nuclear spin–spin couplings within the polarization propagator approach

We present a relativistic theory for the nuclear spin–spin coupling tensor within the polarization propagator approach using the particle-hole Dirac–Coulomb–Breit Hamiltonian and the full four-component wave function. We give explicit expressions for the coupling tensor in the random-phase approximation, neglecting the Breit interaction. A purely relativistic perturbative electron–nuclear Hamiltonian is used and it is shown how the single relativistic contribution to the coupling tensor reduces to Ramsey's three second-order terms (Fermi contact, spin–dipole, and paramagnetic spin–orbit) in the nonrelativistic limit. The principal propagator becomes complex and the leading property integrals mix atomic orbitals of different parity. The well-known propagator expressions for the coupling tensor in the nonrelativistic limit is obtained neglecting terms of the order c^?n (n ? 1). © 1993 John Wiley & Sons, Inc.