Accurate ab initio potential energy surfaces for the (3)A '' and (3)A ' electronic states of the O(P-3) plus HBr system

In this work, we report the construction of potential energy surfaces for the (3)A '' and (3)A' states of the system O(P-3) + HBr. These surfaces are based on extensive ab initio calculations employing the MRCI+Q/CBS+SO level of theory. The complete basis set energies were estimated from extrapolation of MRCI+Q/aug-cc-VnZ(-PP) (n = Q, 5) results and corrections due to spin-orbit effects obtained at the CASSCF/aug-cc-pVTZ(-PP) level of theory. These energies, calculated over a region of the configuration space relevant to the study of the reaction O(P-3) + HBr -> OH + Br, were used to generate functions based on the many-body expansion. The three-body potentials were interpolated using the reproducing kernel Hilbert space method. The resulting surface for the (3)A '' electronic state contains van der Waals minima on the entrance and exit channels and a transition state 6.55 kcal/mol higher than the reactants. This barrier height was then scaled to reproduce the value of 5.01 kcal/mol, which was estimated from coupled cluster benchmark calculations performed to include high-order and core-valence correlation, as well as scalar relativistic effects. The (3)A' surface was also scaled, based on the fact that in the collinear saddle point geometry these two electronic states are degenerate. The vibrationally adiabatic barrier heights are 3.44 kcal/mol for the (3)A '' and 4.16 kcal/mol for the (3)A' state. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4705428]

A novel self consistent calculation approach for the capacitance-voltage characteristics of semiconductor quantum wire transistors based on a split-gate configuration

Purpose - The purpose of this paper is to develop an efficient numerical algorithm for the self-consistent solution of Schrodinger and Poisson equations in one-dimensional systems. The goal is to compute the charge-control and capacitance-voltage characteristics of quantum wire transistors. Design/methodology/approach - The paper presents a numerical formulation employing a non-uniform finite difference discretization scheme, in which the wavefunctions and electronic energy levels are obtained by solving the Schrodinger equation through the split-operator method while a relaxation method in the FTCS scheme ("Forward Time Centered Space") is used to solve the two-dimensional Poisson equation. Findings - The numerical model is validated by taking previously published results as a benchmark and then applying them to yield the charge-control characteristics and the capacitance-voltage relationship for a split-gate quantum wire device. Originality/value - The paper helps to fulfill the need for C-V models of quantum wire device. To do so, the authors implemented a straightforward calculation method for the two-dimensional electronic carrier density n(x,y). The formulation reduces the computational procedure to a much simpler problem, similar to the one-dimensional quantization case, significantly diminishing running time.

VCD to determine absolute configuration of natural product molecules: secolignans from Peperomia blanda

The absolute configuration and solution-state conformers of three peperomin-type secolignans isolated from Peperomia blanda (Piperaceae) are unambiguously determined by using vibrational circular dichroism (VCD) spectroscopy associated with density functional theory (DFT) calculations. Advantages of VCD over the electronic form of CD for the analysis of diastereomers are also discussed. This work extends our growing knowledge about secondary metabolites within the Piperaceae family species while providing a definitive and straightforward method to assess the absolute stereochemistry of secolignans.

In-plane mapping of buried InGaAs quantum rings and hybridization effects on the electronic structure

This work reports the investigation on the structural differences between InAs quantum rings and their precursor quantum dots species as well as on the presence of piezoelectric fields and asymmetries in these nanostructures. The experimental results show significant reduction in the ring dimensions when the sizes of capped and uncapped ring and dot samples are compared. The iso-lattice parameter mapped by grazing-incidence x-ray diffraction has revealed the lateral extent of strained regions in the buried rings. A comparison between strain and composition of dot and ring structures allows inferring on how the ring formation and its final configuration may affect optical response parameters. Based on the experimental observations, a discussion has been introduced on the effective potential profile to emulate theoretically the ring-shape confinement. The effects of confinement and strain field modulation on electron and hole band structures are simulated by a multiband k.p calculation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4733964]

Structure and electronic properties of hydrated mesityl oxide: a sequential quantum mechanics/molecular mechanics approach

The hydration of mesityl oxide (MOx) was investigated through a sequential quantum mechanics/molecular mechanics approach. Emphasis was placed on the analysis of the role played by water in the MOx syn-anti equilibrium and the electronic absorption spectrum. Results for the structure of the MOx-water solution, free energy of solvation and polarization effects are also reported. Our main conclusion was that in gas-phase and in low-polarity solvents, the MOx exists dominantly in syn-form and in aqueous solution in anti-form. This conclusion was supported by Gibbs free energy calculations in gas phase and in-water by quantum mechanical calculations with polarizable continuum model and thermodynamic perturbation theory in Monte Carlo simulations using a polarized MOx model. The consideration of the in-water polarization of the MOx is very important to correctly describe the solute-solvent electrostatic interaction. Our best estimate for the shift of the pi-pi* transition energy of MOx, when it changes from gas-phase to water solvent, shows a red-shift of -2,520 +/- 90 cm(-1), which is only 110 cm(-1) (0.014 eV) below the experimental extrapolation of -2,410 +/- 90 cm(-1). This red-shift of around -2,500 cm(-1) can be divided in two distinct and opposite contributions. One contribution is related to the syn -> anti conformational change leading to a blue-shift of similar to 1,700 cm(-1). Other contribution is the solvent effect on the electronic structure of the MOx leading to a red-shift of around -4,200 cm(-1). Additionally, this red-shift caused by the solvent effect on the electronic structure can by composed by approximately 60 % due to the electrostatic bulk effect, 10 % due to the explicit inclusion of the hydrogen-bonded water molecules and 30 % due to the explicit inclusion of the nearest water molecules.

The radical SeCl: A theoretical contribution to the characterization of its low-lying electronic states

All doublet and quartet electronic states correlating with the first dissociation channel of SeCl and some Rydberg states are investigated theoretically at the CASSCF/MRCI level of theory using extended basis sets, including the contribution of spin-orbit effects. The similarity of the potential energy curves with those of SeF suggests that spectroscopic constants for the ground (X (2)Pi) and the first excited quartet (a(4)Sigma) of SeCl could also be determined via an emission resulting from the reaction of selenium with atomic chlorine. The coupling constant of the ground state at R-e is estimated as -1610 cm (1). The potential energy curves calculated and the derived spectroscopic constants do not support the interpretation and assignment of the scarce transitions recorded experimentally as due to (2)Pi-(2)Pi emissions. That the few observed lines might arise from transitions from the state b(4)Sigma(-)(1/2) to a very high vibrational level of the state a(4)Sigma(-)(1/2) is an open possibility, however, the number of vibrational states and the calculated Delta G(1/2) differ significantly from the reported ones. (C) 2012 Elsevier B. V. All rights reserved.

Electronic and magnetic properties of SnO2/CrO2 thin superlattices

In this article, using first-principles electronic structure calculations within the spin density functional theory, alternated magnetic and non-magnetic layers of rutile-CrO2 and rutile-SnO2 respectively, in a (CrO2) n (SnO2) n superlattice (SL) configuration, with n being the number of monolayers which are considered equal to 1, 2, ..., 10 are studied. A half-metallic behavior is observed for the (CrO2) n (SnO2) n SLs for all values of n. The ground state is found to be FM with a magnetic moment of 2 μB per chromium atom, and this result does not depend on the number of monolayers n. As the FM rutile-CrO2 is unstable at ambient temperature, and known to be stabilized when on top of SnO2, the authors suggest that (CrO2) n (SnO2) n SLs may be applied to spintronic technologies since they provide efficient spin-polarized carriers.