Electronic structure and chemical bonding in W(2) molecule

The electronic structure of the lowest-lying electronic states of W(2) were investigated at the CASPT2 level. The ground state is a X(1)Sigma(+)(g) state, followed by the a(3)Delta(u), b(3)Sigma(+)(u) and A(1)Delta(u) electronic states. Seven low-lying Omega-states were computed: (1)0(g)(+), (2)3(u), (3)2(u), (4)1(u), (5)0(u)(-), (6)1(u), and (7)2(u), with the ground state corresponding to the (1)0(g)(+)(X(1)Sigma(+)(g)) state. Comparison with the other VIB transition metal group dimers indicates a common pattern of electronic structure and spectroscopic properties. (C) 2010 Elsevier B.V. All rights reserved.

Electronic Structure and Chemical Bonding in the Lowest Electronic States of TcN

Multiconfiguration second-order perturbation theory, with the inclusion of relativistic effects and spin-orbit Coupling, was employed to investigate the nature of the ground and low-lying Lambda-S and Omega states of the TcN molecule. Spectroscopic constants, effective bond order, and potential energy curves for 13 low-lying Lambda-S states and 5 Omega states are given, The computed ground state of TcN is of Omega = 3 symmetry (R(e) = 1.605 angstrom and omega(e) = 1085 cm(-1)), originating mainly from the (3)Delta Lambda-S ground state. This result is contrasted with the nature of the ground state for other VIIB transtion-metal mononitrides, including X(3)Sigma(-) symmetry for MnN and Omega = 0(+) symmetry for ReN, derived also from a X(3)Sigma(-) state.

The intramolecular charge transfer in a donor-pi-acceptor dianion probed by resonance Raman spectroscopy and quantum chemical calculations

The dideprotonation of 4-(4-nitrophenylazo)resorcinol generates an anionic species with substantial electronic pi delocalization. As compared to the parent neutral species, the anionic first excited electronic transition, characterized as an intramolecular charge transfer (ICT) from the CO(-) groups to the NO(2) moiety, shows a drastic red shift of ca. 200 nm in the lambda(max) in the UV-vis spectrum, leading to one of the lowest ICT energies observed (lambda(max) = 630 nm in dimethyl sulfoxide (DMSO)) in this class of push-pull molecular systems. Concomitantly, a threefold increase in the molar absorptivity (epsilon(max)) in comparison to the neutral species is observed. The resonance Raman enhancement profiles reveal that in the neutral species the chromophore involves several modes, as nu(C-N), nu(N=N), nu(C=C) and nu(s)(NO(2)), whereas in the dianion, there is a selective enhancement of the NO(2) vibrational modes. The quantum chemical calculations of the electronic transitions and vibrational wavenumbers led to a consistent analysis of the enhancement patterns observed in the resonance Raman spectra. Copyright (C) 2009 John Wiley & Sons, Ltd.

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.

New Relativistic Atomic Natural Orbital Basis Sets for Lanthanide Atoms with Applications to the Ce Diatom and LuF3

New basis sets of the atomic natural orbital (ANO) type have been developed for the lanthanide atoms La-Lu. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies and some excitation energies. Computed ionization energies have an accuracy better than 0.1 eV in most cases. Two molecular applications are inluded as illustration: the cerium diatom and the LuF3 molecule. In both cases it is shown that 4f orbitals are not involved in the chemical bond in contrast to an earlier claim for the latter molecule.

Electronic Structure and Chemical Bonding in the Ground and Low-Lying Electronic States of Ta(2)

The electronic structure and chemical bonding of the ground and low-lying Lambda - S and Omega states of Ta(2) were investigated at the multiconfiguration second-order perturbation theory (CASSCF//CASPT2) level. The ground state of Ta(2) is computed to be a X(3)Sigma(-)(g) state (R(e) = 2.120 angstrom, omega(e) = 323 cm(-1), and D(e) = 4.65 eV), with two low-lying singlet states close to it (a(1) Sigma(+)(g) : T(e) = 409 cm(-1), R(e) = 2.131 angstrom, and omega(e) = 313 cm(-1); b(1) Gamma(g): T(e) = 1, 038 cm(-1), R(e) = 2.127 angstrom, and omega(e) = 316 cm(-1)). These electronic states are derived from the same electronic configuration: vertical bar 13 sigma(2)(g)14 sigma(2)(g)7 delta(2)(g)13 pi(4)(u)>. The effective bond order of the X(3) Sigma(-)(g) state is 4.52, which indicates that the Ta atoms are bound by a quintuple chemical bond. The a(1) Sigma(+)(g) state interacts strongly with the X(3)Sigma(-)(g) g ground state by a second-order spin-orbit interaction, giving rise to the (1)0(g)(+) (ground state) (dominated by the X(3)Sigma(-)(g) Lambda - S ground state) and (9)0(g)(+) (dominated by the a(1) Sigma(+)(g) Lambda - S state) Omega states. These results are in line with those reported for the group 5B homonuclear transition metal diatomics. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1306-1315, 2011

Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

Low-lying singlet and triplet electronic states of RhB

The low-lying X-1 Sigma(+), a(3)Delta, A(1)Delta, b(3)Sigma(+), B-1 Pi, c(3)Pi, C-1 Phi, D-1 Sigma(+), E-1 Pi, d(1)Phi, and e(3)Pi electronic states of RhB have been investigated at the ab initio level, using the multistate multiconfigurational second-order perturbation (MS-CASPT2) theory, with extended atomic basis sets and inclusion of scalar relativistic effects. Among the eleven electronic states included in this work, only three (the X-1 Sigma(+), D-1 Sigma(+), and E-1 Pi states) have been investigated experimentally. Potential energy curves, spectroscopic constants, dipole moments, binding energies, and chemical bonding aspects are presented for all electronic states.

On the Relaxation Mechanisms of 6-Azauracil

The nonadiabatic photochemistry of 6-azauracil has been studied by means of the CASPT2//CASSCF protocol and double-zeta plus polarization ANO basis sets. Minimum energy states, transition states, minimum energy paths, and surface intersections have been computed in order to obtain an accurate description of several potential energy hypersurfaces. It is concluded that, after absorption of ultraviolet radiation (248 nm), two main relaxation mechanisms may occur, via which the lowest (3)(pi pi*) state can be populated. The first one takes place via a conical intersection involving the bright (1)(pi pi*) and the lowest (1)(n pi*) states, ((1)pi pi*/(1)n pi*)(CI), from which a low energy singlet-triplet crossing, ((1)n pi*/(3)pi pi*)(STC), connecting the (1)(n pi*) state to the lowest (3)(pi pi*) triplet state is accessible. The second mechanism arises via a singlet-triplet crossing, ((1)pi pi*/(3)n pi*)(STC), leading to a conical intersection in the triplet manifold, ((3)n pi*/(3)pi pi*)(CI), evolving to the lowest (3)(pi pi*) state. Further radiationless decay to the ground state is possible through a (gs/(3)pi pi*)(STC).

A theoretical study of the binding and electronic spectrum of the Mo-2 molecule

Multiconfigurational SCF and second-order perturbation theory have been employed to study seven low-lying singlet and triplet electronic states of the Mo-2 molecule. The bond order of the ground state has been analyzed based on the effective bond order (EBO), indicating that a fully developed sextuple bond is formed between the two Mo atoms. The experimentally observed excited states a(3)Sigma(+)(u) and A(1)Sigma(+)(u) have been determined and the so-called (3)Lambda excited state identified as the b(3)Sigma(+)(u) state, in agreement with experimental expectations. (C) 2007 Elsevier B.V. All rights reserved.

Perturbation treatment of symmetry breaking within random matrix theory

We discuss the applicability, within the random matrix theory, of perturbative treatment of symmetry breaking to the experimental data on the flip symmetry breaking in quartz crystal. We found that the values of the parameter that measures this breaking are different for the spacing distribution as compared to those for the spectral rigidity. We consider both two-fold and three-fold symmetries. The latter was found to account better for the spectral rigidity than the former. Both cases, however, underestimate the experimental spectral rigidity at large L. This discrepancy can be resolved if an appropriate number of eigenfrequencies is considered to be missing in the sample. Our findings are relevant for symmetry violation studies in general. (C) 2008 Elsevier B.V. All rights reserved.

Decision theory applied to image quality control in radiology

Background: The present work aims at the application of the decision theory to radiological image quality control ( QC) in diagnostic routine. The main problem addressed in the framework of decision theory is to accept or reject a film lot of a radiology service. The probability of each decision of a determined set of variables was obtained from the selected films. Methods: Based on a radiology service routine a decision probability function was determined for each considered group of combination characteristics. These characteristics were related to the film quality control. These parameters were also framed in a set of 8 possibilities, resulting in 256 possible decision rules. In order to determine a general utility application function to access the decision risk, we have used a simple unique parameter called r. The payoffs chosen were: diagnostic's result (correct/incorrect), cost (high/low), and patient satisfaction (yes/no) resulting in eight possible combinations. Results: Depending on the value of r, more or less risk will occur related to the decision-making. The utility function was evaluated in order to determine the probability of a decision. The decision was made with patients or administrators' opinions from a radiology service center. Conclusion: The model is a formal quantitative approach to make a decision related to the medical imaging quality, providing an instrument to discriminate what is really necessary to accept or reject a film or a film lot. The method presented herein can help to access the risk level of an incorrect radiological diagnosis decision.

Approximation to density functional theory for the calculation of band gaps of semiconductors

The local-density approximation (LDA) together with the half occupation (transitionstate) is notoriously successful in the calculation of atomic ionization potentials. When it comes to extended systems, such as a semiconductor infinite system, it has been very difficult to find a way to half ionize because the hole tends to be infinitely extended (a Bloch wave). The answer to this problem lies in the LDA formalism itself. One proves that the half occupation is equivalent to introducing the hole self-energy (electrostatic and exchange correlation) into the Schrodinger equation. The argument then becomes simple: The eigenvalue minus the self-energy has to be minimized because the atom has a minimal energy. Then one simply proves that the hole is localized, not infinitely extended, because it must have maximal self-energy. Then one also arrives at an equation similar to the self- interaction correction equation, but corrected for the removal of just 1/2 electron. Applied to the calculation of band gaps and effective masses, we use the self- energy calculated in atoms and attain a precision similar to that of GW, but with the great advantage that it requires no more computational effort than standard LDA.

Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M(13). First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first- principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M(13) structures. Several new lower energy configurations were identified, e. g., Pd(13), W(13), Pt(13), etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au(13), we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.

New simple and efficient heuristics for the uncapacitated single allocation hub location problem

Hub-and-spoke networks are widely studied in the area of location theory. They arise in several contexts, including passenger airlines, postal and parcel delivery, and computer and telecommunication networks. Hub location problems usually involve three simultaneous decisions to be made: the optimal number of hub nodes, their locations and the allocation of the non-hub nodes to the hubs. In the uncapacitated single allocation hub location problem (USAHLP) hub nodes have no capacity constraints and non-hub nodes must be assigned to only one hub. In this paper, we propose three variants of a simple and efficient multi-start tabu search heuristic as well as a two-stage integrated tabu search heuristic to solve this problem. With multi-start heuristics, several different initial solutions are constructed and then improved by tabu search, while in the two-stage integrated heuristic tabu search is applied to improve both the locational and allocational part of the problem. Computational experiments using typical benchmark problems (Civil Aeronautics Board (CAB) and Australian Post (AP) data sets) as well as new and modified instances show that our approaches consistently return the optimal or best-known results in very short CPU times, thus allowing the possibility of efficiently solving larger instances of the USAHLP than those found in the literature. We also report the integer optimal solutions for all 80 CAB data set instances and the 12 AP instances up to 100 nodes, as well as for the corresponding new generated AP instances with reduced fixed costs. Published by Elsevier Ltd.