Time-dependent density-functional calculations for optical spectra of Na-2 and Na-4 clusters

With the frame of the time-dependent local density approximation, an efficient description of the optical response of clusters has been used to study the photo-absorption cross section of Na-2 and Na-4 clusters. It is shown that our calculated results are in good agreement with the experiment. In addition, our calculated spectrum for the Na-4 cluster is in better agreement with experiment than the GW absorption spectrum.

Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to Alkynes

The B3LYP hybrid density functional method has been carried Out to Study theoretically the mechanisin of Pd(0)-catalyzed alkyne cyanoboration reaction. Both the intermolecular and intramolecular alkyne cyanoboration reactions were studied. For each reaction, three paths were proposed. In path A of each reaction, the first step is B-CN bond oxidative addition to bisphosphine complex Pd(PH3)(2), in path B of each reaction, the first step is alkyne coordination to bisphosphine complex Pd(PH3)2, and in path C of each reaction, the first step is the PH3 dissociation front Pd(PH3)2 to form monophosphine complex Pd(PH3) For both reactions, path B is favored.

Magnetic and electronic properties of CaCu3Cr4O12 and CaCu3Cr2Sb2O12 by first-principles density functional calculation

The electronic and magnetic properties of CaCu3Cr4O12 and CaCu3Cr2Sb2O12 are investigated by the use of the full-potential linearized augumented plane wave (FPLAPW) method. The calculated results indicate that CaCu3- Cr4O12 is a ferrimagnetic and half-metallic compound, in good agreement with previous theoretical studies. CaCu3- Cr2Sb2O12 is a ferrimagnetic semiconductor with a small gap of 0.136 eV. In both compounds, because Cr4+ 3d (d(2)) and Cr3+ 3d (d(3)) orbitals are less than half filled, the coupling between Cr-Cu is antiferromagnetic, whereas that between Cu-Cu and Cr-Cr is ferromagnetic. The total net spin moment is 5.0 and 3.0 mu(B) for CaCu3Cr4O12 and CaCu3Cr2Sb2O12, respectively. In CaCu3Cr4O12, the 3d electrons of Cr4+ are delocalized, which strengthens the Cr-Cr ferromagnetic coupling. For CaCu3Cr2Sb2O12, the doping of nonmagnetic ion Sb5+ reduces the Cr-Cr ferromagnetic coupling, and the half-filled Cr3+ t(2g) (t(2g)(3)) makes the chromium 3d electrons localized. In addition, the ordering arrangement of the octahedral chromium and antimony ions also prevents the delocalization of electrons. Hence, CaCu3Cr2Sb2O12 shows insulating behavior, in agreement with the experimental observation.

Density-functional study of lanthanum, ytterbium, and lutetium dimers

La-2, Yb-2, and Lu-2 have been studied by use of the density-functional methods B3LYP, BLYP, B3PW91, BHLYP, BP86, B3P86, MPW1PW91, and PBE1PBE. In these density-functional methods, the exchange functional is from either Becke's three-parameter HF-DFT hybrid exchange functional (B3), pure DFT exchange functional of 1988 (B), a modification of the half-and-half HF/DFT hybrid method (BH), Perdew-Wang 1991 (PW91), or Barone's modified PW91 (MPW1), while the correlation functional is from either Lee, Yang, and Parr (LYP), Perdew-Wang 1991 (PW91), or Perdew 86 (P86). PBE1PBE is the generalized-gradient-approximation exchange-correlation functional of Perdew, Burke, and Ernzerhof. For La-2, the calculated bond distance is in reasonable agreement with the experiment, but the calculated vibrational frequency is underestimated significantly compared with the experiment. Only BP86 and B3P86 have the best performance in reproducing the experimental dissociation energy for La-2. For the van der Waals dimer Yb-2, three functionals, B3LYP, BLYP, and BHLYP have excellent performance in reproducing the spectroscopic constants compared with both the experiment and previous theoretical studies.

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.

Abnormal ferroelectric response and enhancement of piezoelectricity of PbTiO3 under uniaxial compression

The ferroelectricity of rhombohedral PbTiO3 under uniaxial compression is investigated from first-principles study. Upon compression, the ferroelectricity decreases until a critical stress of -29 GPa and then increases with a further increase of the magnitude of the uniaxial compressive stress. We also find that uniaxial compression could enhance piezoelectricity and that the maximum piezoelectric coefficient d(33) occurs at sigma(33)=-49 GPa, which supports the experimentally observed piezoelectric behavior in rhombohedral Pb(Mg1/3Nb2/3O3)-0.32PbTiO(3) [Q. Wan, C. Chen, and Y. P. Shen, J. Appl. Phys. 98, 024103 (2005)]. Our calculated results show that the Pb, Ti, and O atoms have different contributions to the total polarization with increasing the magnitude of uniaxial compressive stress, and that when -sigma(33)>55 GPa, the Ti atoms no longer have contributions to the polarization, which leads to the changes of ferroelectricity and piezoelectricity. (C) 2008 American Institute of Physics.

Studies of tetragonal PbTiO3 subjected to uniaxial stress along the c-axis

Tetragonal PbTiO3 under uniaxial stress along the c-axis is investigated from first-principles. The structural parameters, polarization, and squares of the lowest optical phonon frequencies for E(1TO) and A(1)(1TO) modes at Gamma show abrupt changes near a stress sigma(c) of 1.04 GPa, which is related to the dramatic change of elastic constant c(33) resulting from the uniaxial stress applied along the c-axis. We also find that the uniaxial compressive stress could enhance the piezoelectric stress coefficients, whereas the uniaxial tensile stress could enhance the piezoelectric strain coefficients. It is also found that when the magnitude of uniaxial compressive stress sigma(33) is greater than 12 GPa, PbTiO3 is transformed to the paraelectric tetragonal phase.

Elasticity, band-gap bowing, and polarization of AlxGa1-xN alloys

Elastic constants, the bulk modulus, Young's modulus, band-gap bowing coefficients, spontaneous and piezoelectric polarizations, and piezoelectric coefficients of hexagonal AlxGa1-xN ternary alloys are calculated using first-principles methods. The fully relaxed structures and the structures subjected to homogeneous biaxial and uniaxial tension are investigated. We show that the biaxial tension in the plane perpendicular to the c axis and the uniaxial tension along the c axis all reduce the bulk modulus, whereas they reduce and enhance Young's modulus, respectively. We find that the biaxial and uniaxial tension can enhance the bowing coefficients. We also find that the biaxial tension can enhance the total polarization, while the uniaxial tension will suppress the total polarization. (C) 2008 American Institute of Physics.