Ab initio configuration-interaction study of the ground and low-lying electronic states of NiI

For the first time, we have studied the potential-energy curves, spectroscopic terms, vibrational levels, and the spectroscopic constants of the ground and low-lying excited states of NiI by employing the complete active space self-consistent-field method with relativistic effective core potentials followed by multireference configuration-interaction calculations. We have identified six low-lying electronic states of NiI with doublet spin multiplicities, including three states of Delta symmetry and three states of Pi symmetry of the molecule within 15 000 cm(-1). The lowest (2)Delta state is identified as the ground state of NiI, and the lowest (2)Pi state is found at 2174.56 cm(-1) above it. These results fully support the previous conclusion of the observed spectra although our computational energy separation of the two states is obviously larger than that of the experimental values. The present calculations show that the low-lying excited states [13.9] (2)Pi and [14.6] (2)Delta are 3 (2)Pi and 3 (2)Delta electronic states of NiI, respectively. Our computed spectroscopic terms, vibrational levels, and spectroscopic constants for them are in good agreement with the experimental data available at present. In the present work we have not only suggested assignments for the observed states but also computed more electronic states that are yet to be observed experimentally. (c) 2005 American Institute of Physics.

Comparison of quantum chemistry calculation methods of nucleic acid base-quartets

Nine base-quartets were calculated by six semi-empirical methods and ab initio Hartree-Fork method using STO-3G basis set. The results showed that PM3 method can be use to calculate base quartets, the results of PM3 calculations are close to the ab initio

Ground state of lutetium dimer by density functional methods

Bond distances, vibrational frequencies and dissociation energies for the ground state of Lu-2 were studied by density functional methods B3LYP, B3PW91, BLYP, BHLYP, BP86, B3P86, MPW1PW91, PBE1PBE and SVWN with CEP-121G and SDD basis sets. Singlet state is predicted to be the most stable. CEP-121G has a better overall performance than SDD. At CEP-121G basis set, all density functional methods used in this study perform well in reproducing the spectroscopic constants.

Mechanical and chemical bonding properties of ground state BeH2

The crystal structure, mechanical properties and electronic structure of ground state BeH2 are calculated employing the first-principles methods based on the density functional theory. Our calculated structural parameters at equilibrium volume are well consistent with experimental results. Elastic constants, which well obey the mechanical stability criteria, are firstly theoretically acquired. The bulk modulus B, Shear modulus G, Young's modulus E, and Poisson's ratio upsilon are deduced from the elastic constants. The bonding nature in BeH2 is fully interpreted by combining characteristics in band structure, density of states, and charge distribution. The ionicity in the Be-H bond is mainly featured by charge transfer from Be 2s to H 1s atomic orbitals while its covalency is dominated by the hybridization of H 1s and Be 2p states. The Bader analysis of BeH2 and MgH2 are performed to describe the ionic/covalent character quantitatively and we find that about 1.61 (1.6) electrons transfer from each Be (Mg) atom to H atoms.

Nitrogen defects and ferromagnetism in Cr-doped dilute magnetic semiconductor AlN from first principles

High Curie temperature of 900 K has been reported in Cr-doped AlN diluted magnetic semiconductors prepared by various methods, which is exciting for spintronic applications. It is believed that N defects play important roles in achieving the high-temperature ferromagnetism in good samples. Motivated by these experimental advances, we use a full-potential density-functional-theory method and supercell approach to investigate N defects and their effects on ferromagnetism of (Al,Cr)N with N vacancies (V-N). We investigate the structural and electronic properties of V-N, single Cr atom, Cr-Cr atom pairs, Cr-V-N pairs, and so on. In each case, the most stable structure is obtained by comparing different atomic configurations optimized in terms of the total energy and the force on every atom, and then it is used to calculate the defect formation energy and study the electronic structures. Our total-energy calculations show that the nearest substitutional Cr-Cr pair with the two spins in parallel is the most favorable and the nearest Cr-V-N pair makes a stable complex. Our formation energies indicate that V-N regions can be formed spontaneously under N-poor condition because the minimal V-N formation energy equals -0.23 eV or Cr-doped regions with high enough concentrations can be formed under N-rich condition because the Cr formation energy equals 0.04 eV, and hence real Cr-doped AlN samples are formed by forming some Cr-doped regions and separated V-N regions and through subsequent atomic relaxation during annealing. Both of the single Cr atom and the N vacancy create filled electronic states in the semiconductor gap of AlN. N vacancies enhance the ferromagnetism by adding mu(B) to the Cr moment each but reduce the ferromagnetic exchange constants between the spins in the nearest Cr-Cr pairs. These calculated results are in agreement with experimental observations and facts of real Cr-doped AlN samples and their synthesis. Our first-principles results are useful to elucidate the mechanism for the ferromagnetism and to explore high-performance Cr-doped AlN diluted magnetic semiconductors.

Effects of residual C and O impurities on photoluminescence in undoped GaN epilayers

Photoluminescence (PL) was investigated in undoped GaN from 4.8 K to room temperature. The 4.8 K spectra exhibited recombinations of free exciton, donor-acceptor pair (DAP), blue and yellow bands (Ybs). The blue band (BB) was also identified to be a DAP recombination. The YB was assigned to a recombination from deep levels. The energy-dispersive X-ray spectroscopy show that C and O are the main residual impurities in undoped GaN and that C concentration is lower in the epilayers with the stronger BB. The electronic structures of native defects, C and O impurities, and their complexes were calculated using ab initio local-density-functional (LDF) methods with linear muffin-tin-orbital and 72-atomic supercell. The theoretical analyses suggest that the electron transitions from O-N states to C-N and to V-Ga states are responsible for DAP and the BB, respectively, and the electron transitions between the inner levels of the C-N-O-N complex may be responsible for the YB in our samples. (C) 2002 Elsevier Science B.V. All rights reserved.

Effects of residual C and O impurities on photoluminescence in undoped GaN epilayers

Photoluminescence (PL) was investigated in undoped GaN from 4.8 K to room temperature. The 4.8 K spectra exhibited recombinations of free exciton, donor-acceptor pair (DAP), blue and yellow bands (Ybs). The blue band (BB) was also identified to be a DAP recombination. The YB was assigned to a recombination from deep levels. The energy-dispersive X-ray spectroscopy show that C and O are the main residual impurities in undoped GaN and that C concentration is lower in the epilayers with the stronger BB. The electronic structures of native defects, C and O impurities, and their complexes were calculated using ab initio local-density-functional (LDF) methods with linear muffin-tin-orbital and 72-atomic supercell. The theoretical analyses suggest that the electron transitions from O-N states to C-N and to V-Ga states are responsible for DAP and the BB, respectively, and the electron transitions between the inner levels of the C-N-O-N complex may be responsible for the YB in our samples. (C) 2002 Elsevier Science B.V. All rights reserved.

Golden-rule treatment on the ClO/ClO+ electron-transfer system

The structures, properties and electron transfer reactivity of the ClO/ClO+ coupling system are studied in this paper at ab initio (HF and MP2) levels and the density functional theory (DFT: B3LYP, B3P86, B3PW91) levels employing 6311 + G(3df) basis set and on the basis of the golden-rule of the time-dependent perturbation theory. Investigations indicate that the results got from the B3LYP method employing 6-311 + G(3df) basis set is in excellent agreement with the experiment. The activation energies, the stabilization energies and the electronic coupling matrix elements have also been calculated by using the B3LYP/6-311 + G(3df) method, and then the electron transfer rates are determined at this level. The electronic coupling matrix element of EC.6 is very small, only 0.03 kcal/mol, while that of EC.7 is the biggest, being 12.41 kcal/mol, the corresponding electron transfer rate is also the fastest among these seven encounter complexes. The averaged electron transfer rate is about 1.672 X 10(11) M-1 s(-1). It is indicated that the structures optimized by B3LYP method are more reliable than the results got from the other four methods. It also testified that the electronic coupling matrix element is the vital factor that significantly affects the electron transfer rate. (C) 2003 Elsevier B.V. All rights reserved.