Electronic structure and chemical bonding in the ground states of Tc(2) and Re(2)

Multiconfiguration second-order perturbation theory, including relativistic effects and spin-orbit coupling, has been employed to investigate the nature of the chemical bonding in the ground state of Tc(2) and Re(2). The Tc(2) ground state is found to be a 0(g)(+) state, with an effective bond order (EBO) of 4.4, and a dissociation energy of 3.25 eV. The Re(2) ground state is a 1(g) state, with EBO = 4.3. Almost degenerate to it, is a 0(g)(+) state (T(e) = 77 cm(-1)), with EBO = 4.1. Experimental evidence also indicates that the ground state is of 1(g) nature. The dissociation energy is computed to be 5.0 eV in agreement with an experimental estimate of 4 +/- 1 eV.

Quantum spin models with exact dimer ground states

Inspired by the exact solution of the Majumdar-Ghosh model, a family of one-dimensional, translationally invariant spin Hamiltonians is constructed. The exchange coupling in these models is antiferromagnetic, and decreases linearly with the separation between the spins. The coupling becomes identically zero beyond a certain distance. It is rigorously proved that the dimer configuration is an exact, superstable ground-state configuration of all the members of the family on a periodic chain. The ground state is twofold degenerate, and there exists an energy gap above the ground state. The Majumdar-Ghosh Hamiltonian with a twofold degenerate dimer ground state is just the first member of the family. The scheme of construction is generalized to two and three dimensions, and illustrated with the help of some concrete examples. The first member in two dimensions is the Shastry-Sutherland model. Many of these models have exponentially degenerate, exact dimer ground states.

类氟体系基态电离能关系的研究；Research on relation of the ionization energy of the ground states of florin-like system

在类氢离子能级相对论修正的基础上,依据屏蔽方法,给出了类氟体系基态电离能的一种表达式.依据原子序数9至20的元素类氟体系基态电离能的实验数据,使用Microcal Origin软件拟合出类氟体系非电离电子平均屏蔽系数与原子序数的函数关系,总结出类氟体系基态电离能遵从的关系式并进行了验证.推算了原子序数21至40的元素类氟离子的基态电离能.

Calculation of nondifferential properties for atomic ground states /

A new method for sampling the exact (within the nodal error) ground state distribution and nondiflPerential properties of multielectron systems is developed and applied to firstrow atoms. Calculated properties are the distribution moments and the electronic density at the nucleus (the 6 operator). For this purpose, new simple trial functions are developed and optimized. First, using Hydrogen as a test case, we demonstrate the accuracy of our algorithm and its sensitivity to error in the trial function. Applications to first row atoms are then described. We obtain results which are more satisfactory than the ones obtained previously using Monte Carlo methods, despite the relative crudeness of our trial functions. Also, a comparison is made with results of highly accurate post-Hartree Fock calculations, thereby illuminating the nodal error in our estimates. Taking into account the CPU time spent, our results, particularly for the 8 operator, have a relatively large variance. Several ways of improving the eflSciency together with some extensions of the algorithm are suggested.

Stability and related properties of vacua and ground states

We consider the formal non-relativistic limit (nrl) of the : phi(4):(s+1) relativistic quantum field theory (rqft), where s is the space dimension. Following the work of R. Jackiw [R. Jackiw, in: A. Ali, P. Hood-bhoy (Eds.), Beg Memorial Volume, World Scientific, Singapore, 1991], we show that, for s = 2 and a given value of the ultraviolet cutoff K, there are two ways to perform the nrl: (i) fixing the renormalized mass m(2) equal to the bare mass m(0)(2); (ii) keeping the renormalized mass fixed and different from the bare mass mo. In the (infinite-volume) two-particle sector the scattering amplitude tends to zero as K -> infinity in case (i) and, in case (ii), there is a bound state, indicating that the interaction potential is attractive. As a consequence, stability of matter fails for our boson system. We discuss why both alternatives do not reproduce the low-energy behaviour of the full rqft. The singular nature of the nrl is also nicely illustrated for s = 1 by a rigorous stability/instability result of a different nature. (C) 2007 Elsevier Inc. All rights reserved.

Measurement-based teleportation along quantum spin chains

We examine the teleportation of an unknown spin-1/2 quantum state along a quantum spin chain with an even number of sites. Our protocol, using a sequence of Bell measurements, may be viewed as an iterated version of the 2-qubit protocol of C. H. Bennett et al. [Phys. Rev. Lett. 70, 1895 (1993)]. A decomposition of the Hilbert space of the spin chain into 4 vector spaces, called Bell subspaces, is given. It is established that any state from a Bell subspace may be used as a channel to perform unit fidelity teleportation. The space of all spin-0 many-body states, which includes the ground states of many known antiferromagnetic systems, belongs to a common Bell subspace. A channel-dependent teleportation parameter O is introduced, and a bound on the teleportation fidelity is given in terms of O.

Teleportation via Multi-Qubit Channels

We investigate the problem of teleporting an unknown qubit state to a recipient via a channel of 2L qubits. In this procedure a protocol is employed whereby L Bell state measurements are made and information based on these measurements is sent via a classical channel to the recipient. Upon receiving this information the recipient determines a local gate which is used to recover the original state. We find that the 2(2L)-dimensional Hilbert space of states available for the channel admits a decomposition into four subspaces. Every state within a given subspace is a perfect channel, and each sequence of Bell measurements projects 2L qubits of the system into one of the four subspaces. As a result, only two bits of classical information need be sent to the recipient for them to determine the gate. We note some connections between these four subspaces and ground states of many-body Hamiltonian systems, and discuss the implications of these results towards understanding entanglement in multi-qubit systems.

Evaluation of solute-solvent interactions from solvent blue-shifts of n → π* transitions of C=O, C=S, NO2 and N=N groups: hydrogen bond energies of various donor-acceptor systems

Effects of non-polar, polar and proton-donating solvents on the n → π* transitions of C=O, C=S, NO2 and N=N groups have been investigated. The shifts of the absorption maxima in non-polar and polar solvents have been related to the electrostatic interactions between solute and solvent molecules, by employing the theory of McRAE. In solvents which can donate protons the solvent shifts are mainly determined by solute-solvent hydrogen bonding. Isobestic points have been found in the n → π* bonds of ethylenetrithio-carbonate in heptane-alcohol and heptane-chloroform solvent systems, indicating the existence of equilibria between the hydrogen bonded and the free species of the solute. Among the different proton-donating solvents studied water produces the largest blue-shifts. The blue-shifts in alcohols decrease in the order 2,2,2-trifluoroethanol, methanol, ethanol, isopropanol and t-butanol, the blue-shift in trifluoroethanol being nearly equal to that in water. This trend is exactly opposite to that for the self-association of alcohols. It is suggested that electron-withdrawing groups not merely decrease the extent of self-association of alcohols, but also increase the ability to donate hydrogen bonds. The approximate hydrogen-bond energies for several donor-acceptor systems have been estimated. In a series of aliphatio ketones and nitro compounds studied, the blue-shifts and consequently the hydrogen bond energies decrease with the decrease in the electron-withdrawing power of the alkyl groups. It is felt that electron-withdrawing groups render the chromophores better proton acceptors, and the alcohols better donors. A linear relationship between n → π* transition frequency and the infrared frequency of ethylenetrithiocarbonate has been found. It is concluded that stabilization of the electronic ground states of solute molecules by electrostatic and/or hydrogen-bond interactions determines the solvent shifts.

Quantum Phase Diagram of One-Dimensional Spin and Hubbard Models with Transitions to Bond Order Wave Phases

Similar quantum phase diagrams and transitions are found for three classes of one-dimensional models with equally spaced sites, singlet ground states (GS), inversion symmetry at sites and a bond order wave (BOW) phase in some sectors. The models are frustrated spin-1/2 chains with variable range exchange, half-filled Hubbard models with spin-independent interactions and modified Hubbard models with site energies for describing organic charge transfer salts. In some range of parameters, the models have a first order quantum transition at which the GS expectation value of the sublattice spin < S-A(2)> of odd or even-numbered sites is discontinuous. There is an intermediate BOW phase for other model parameters that lead to two continuous quantum transitions with continuous < S-A(2)>. Exact diagonalization of finite systems and symmetry arguments provide a unified picture of familiar 1D models that have appeared separately in widely different contexts.

Quantum Phase Diagram of One-Dimensional Spin and Hubbard Models with Transitions to Bond Order Wave Phases

Similar quantum phase diagrams and transitions are found for three classes of one-dimensional models with equally spaced sites, singlet ground states (GS), inversion symmetry at sites and a bond order wave (BOW) phase in some sectors. The models are frustrated spin-1/2 chains with variable range exchange, half-filled Hubbard models with spin-independent interactions and modified Hubbard models with site energies for describing organic charge transfer salts. In some range of parameters, the models have a first order quantum transition at which the GS expectation value of the sublattice spin < S-A(2)> of odd or even-numbered sites is discontinuous. There is an intermediate BOW phase for other model parameters that lead to two continuous quantum transitions with continuous < S-A(2)>. Exact diagonalization of finite systems and symmetry arguments provide a unified picture of familiar 1D models that have appeared separately in widely different contexts.

Alpha-decay for heavy nuclei in the ground and isomeric states

The alpha-decay half-lives of nuclei in the ground states and Isomeric states have been calculated within the WKB approximation and Royer's formulas. The barrier in the quasimolecular shape path is determined within a generalized liquid drop model (GLDM). in which the centrifugal potential energy has been introduced to study the unfavored a-decay The agreement between the calculated results and experimental data indicates the reliability of studying alpha-decay of isomeric states with the generalized liquid drop model We find that their is no significant difference of preformation probability between Isomeric states and the corresponding ground states generally in favored alpha-decay Additionally. we extended Royer's formulas by taking account of the role of centrifugal harrier to study the unfavored alpha-decay, and some predicts oil the a decay half-lives of Isomers are made Finally. the effects of angular momontum transfer and Q(alpha) on alpha-decay half-life have been discussed Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved

Ground and Electronic Excited States from Pairing Matrix Fluctuation and Particle-Particle Random Phase Approximation

The accurate description of ground and electronic excited states is an important and challenging topic in quantum chemistry. The pairing matrix fluctuation, as a counterpart of the density fluctuation, is applied to this topic. From the pairing matrix fluctuation, the exact electron correlation energy as well as two electron addition/removal energies can be extracted. Therefore, both ground state and excited states energies can be obtained and they are in principle exact with a complete knowledge of the pairing matrix fluctuation. In practice, considering the exact pairing matrix fluctuation is unknown, we adopt its simple approximation --- the particle-particle random phase approximation (pp-RPA) --- for ground and excited states calculations. The algorithms for accelerating the pp-RPA calculation, including spin separation, spin adaptation, as well as an iterative Davidson method, are developed. For ground states correlation descriptions, the results obtained from pp-RPA are usually comparable to and can be more accurate than those from traditional particle-hole random phase approximation (ph-RPA). For excited states, the pp-RPA is able to describe double, Rydberg, and charge transfer excitations, which are challenging for conventional time-dependent density functional theory (TDDFT). Although the pp-RPA intrinsically cannot describe those excitations excited from the orbitals below the highest occupied molecular orbital (HOMO), its performances on those single excitations that can be captured are comparable to TDDFT. The pp-RPA for excitation calculation is further applied to challenging diradical problems and is used to unveil the nature of the ground and electronic excited states of higher acenes. The pp-RPA and the corresponding Tamm-Dancoff approximation (pp-TDA) are also applied to conical intersections, an important concept in nonadiabatic dynamics. Their good description of the double-cone feature of conical intersections is in sharp contrast to the failure of TDDFT. All in all, the pairing matrix fluctuation opens up new channel of thinking for quantum chemistry, and the pp-RPA is a promising method in describing ground and electronic excited states.

Stereoselectivity in the addition of hydrogen chloride to cyclohex-1-enecarbonitrile: Possible role of chlorine lone pair-nitrile π-orbital pseudoallylic A1, 3 interaction

The (overall trans) addition of hydrogen chloride to cyclohex-1- enecarbonitrile in anhydrous alcoholic media proceeds to give cis-2-chlorocyclohexanecarboxylate (together with some cis-2- chlorocyclohexanecarboxamide): no corresponding products with the trans-configuration are detectable. In anhydrous ether the addition proceeds to give a single isomer, presumably cis-, of 2-chlorocyclohexanecarbonitrile, indicating that the configuration of the products may not be equilibrium-controlled in alcoholic media. An examination of the steric factors indicates that the transition state for protonation of the presumed intermediate, 2-chlorocyclohexylidenemethylideneimine, leading to cis-product is favoured if interaction between the lateral π-orbital of the C-N double bond and the lone-pairs on the chlorine atom at the 2-position is large. Consideration of interactions in the transition states meets Zimmerman's criticism that invoking A1, 3 interaction existing in ground states to explain product configuration takes insufficient account of the Curtin-Hammett principle.

Zero-point entropy in 'spin ice'

Common water ice (ice I-h) is an unusual solid-the oxygen atoms form a periodic structure but the hydrogen atoms are highly disordered due to there being two inequivalent O-H bond lengths'. Pauling showed that the presence of these two bond lengths leads to a macroscopic degeneracy of possible ground states(2,3), such that the system has finite entropy as the temperature tends towards zero. The dynamics associated with this degeneracy are experimentally inaccessible, however, as ice melts and the hydrogen dynamics cannot be studied independently of oxygen motion(4). An analogous system(5) in which this degeneracy can be studied is a magnet with the pyrochlore structure-termed 'spin ice'-where spin orientation plays a similar role to that of the hydrogen position in ice I-h. Here we present specific-heat data for one such system, Dy2Ti2O7, from which we infer a total spin entropy of 0.67Rln2. This is similar to the value, 0.71Rln2, determined for ice I-h, SO confirming the validity of the correspondence. We also find, through application of a magnetic field, behaviour not accessible in water ice-restoration of much of the ground-state entropy and new transitions involving transverse spin degrees of freedom.

Tuning nuclearity of clusters by positional change of functional group: Synthesis of polynuclear clusters, crystal structures and magnetic properties

Four neutral polynuclear magnetic clusters, (Mn6Mn2Na2I)-Mn-III-Na-II(N-3)(8)(mu(1)-O)(2)(L-1)(6)(CH3OH)(2)] (1), (Mn6Na2I)-Na-III(N-3)(4)(mu(4)-O)(2)(L-2)(4)(CH3COO)(4)] (2), Ni-5(II)(N-3)(4)(HL1)(4)(HCOO)(2)(CH3OH)(2)(H2O)(2)]center dot 2CH(3)OH (3) and (Ni4Na2I)-Na-II(N-3)(4)(HL2)(6)]center dot 2CH(3)OH (4) have been synthesized using tetradentate ligands H2L1-2 along with azide as a co-ligand. H2L1-2 are the products formed in situ upon condensation of 2-hydroxy-3-methoxybenzaldehyde with 1-aminopropan-2-ol and 1-aminopropan-3-ol, respectively. Single crystal X-ray diffraction and bond valence sum calculation showed that complex 1 is composed of both Mn-III and Mn-II. Complex 3 contains coordinated formate, which was formed upon in situ oxidation of methanol. The magnetic study over a wide range of temperatures of all the complexes (1-4) showed that 1 and 2 are antiferromagnetic whereas other two (3-4) are predominantly ferromagnetic. The estimated ground states of the complexes are S approximate to 3(1), S = 4(2), S = 5(3) and S approximate to 4(4), respectively. (C) 2014 Elsevier B.V. All rights reserved.