Ab Initio Calculations of the Electronic Structures of Copper Pyrites CuS2, CuSe2 and CuTe2

The electronic structures of CuS2, CuSe2 and CuTe2 with pyrite structures, within the framework the density-functional theory have been investigated. The calculated results explained the recent experimental results which show that there is no clear indication of strong electron correlations in the electronic properties of Cu pyrites, due to the dominant chalcogen p character rather than d characteristic of Cu at the Fermi level.

Ab initio calculations of accurate dissociation energy and analytic potential energy function for the second excited state B^1∏ of ^7LiH

The reasonable dissociation limit of the second excited singlet state B1∏ of ^7LiH molecule is obtained. The accurate dissociation energy and equilibrium geometry of the B^∏ state are calculated using a symmetry-adaptedcluster configuration interaction method in full active space. The whole potential energy curve for the B1H state is obtained over the internuclear distance ranging from about 0.10 nm to 0,54 nm, and has a least-square fit to the analytic Murrell-Sorbie function form. The vertical excitation energy is calculated from the ground state to the B^1∏ state and compared with previous theoretical results. The equilibrium internuclear distance obtained by geometry optimization is found to be quite different from that obtained by single-point energy scanning under the same calculation condition. Based on the analytic potential energy function, the harmonic frequency value of the B^1∏ state is estimated. A comparison of the theoretical calculations of dissociation energies, equilibrium interatomic distances and the analytic potential energy function with those obtained by previous theoretical results clearly shows that the present work is more comprehensive and in better agreement with experiments than previous theories, thus it is an improvement on previous theories.

Investigation of hydrogen bonding in neat dimethyl sulfoxide and binary mixture(dimethyl sulfoxide + water) by concentration-dependent Raman study and ab initio calculation

In this study, our vibrational spectroscopic analysis is made on hydrogen-bonding between dimethyl sulfoxide and water comprises both experimental Raman spectra and ab initio calculations on structures of various dimethyl sulfoxide/water clusters with increasing water content. The Raman peak position of the v（S=O） stretching mode of dimethyl sulfoxide serves as a probe for monitoring the degree of hydrogen-bonding between dimethyl sulfoxide and water. In addition, the two vibrational modes, namely, the CH3 symmetric stretching mode and the CH3 asymmetric stretching mode have been analysed under different concentrations. We relate the computational results to the experimental vibrational wavenumber trends that are observed in our concentration-dependent Raman study. The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the nature of the hydrogen bonding and the structures of the hydrogen-bonded complexes studied.

Ab initio calculation of accurate dissociation energy, potential energy curve and dipole moment function for the A^1∑＋ state ^7LiH molecule

The reasonable dissociation limit of the A^1∑＋ state ^7LiH molecule is obtained. The accurate dissociation energy and the equilibrium geometry of this state are calculated using a symmetry-adapted-cluster configuration-interaction method in complete active space for the first time, The whole potential energy curve and the dipole moment function for the A^1∑＋ state are calculated over a wide internuclear separation range from about 0.1 to 1.4 nm. The calculated equilibrium geometry and dissociation energy of this potential energy curve are of Re=0.2487 nm and De=1.064eV, respectively. The unusual negative values of the anharmonicity constant and the vibration-rotational coupling constant are of ωeXe=-4.7158cm^-1 and αe=0.08649cm^-1, respectively. The vertical excitation energy from the ground to the A^1∑＋ state is calculated and the value is of 3.613eV at 0.15875nm （the equilibrium position of the ground state）. The highly anomalous shape of this potential energy curve, which is exceptionally flat over a wide radial range around the equilibrium position, is discussed in detail. The harmonic frequency value of 502.47cm^-1 about this state is approximately estimated. Careful comparison of the theoretical determinations with those obtained by previous theories about the A^1∑＋ state dissociation energy clearly shows that the present calculations are much closer to the experiments than previous theories, thus represents an improvement.

Ab initio calculation of the growth of Te nanorods and Bi_2Te_3 nanoplatelets

In this paper the growth mechanism of a Te/Bi2Te3 novel structure is studied by ab-initio calculations. The results show that the growth of Te nanorods is determined by the adsorption energy of Te atoms on different crystalline Te surfaces. The adsorption energy of Te on the Te （001） surface is 3.29 eV, which is about 0.25 eV higher than that of Te on the Te （110）. This energy difference makes the preferential growth direction along the 〈 001 〉 direction. In addition, the higher surface energy of Bi2Te3 （110） and the lattice misfit between crystalline Bi2We3 and Te along 〈 001 〉 direction are considered to explain the growth of the Bi2Te3 nanoplatelets, in which Volmer-Weber model is used. The theoretical results are in agreement with experimental observation.

Ab initio calculations on the spectroscopic constants, vibrational levels and classical turning points for the 2^1Пu state of dimer ^7Li2

The accurate dissociation energy and harmonic frequency for the highly excited 2^1Пu state of dimer ^7Li2 have been calculated using a symmetry-adapted-cluster configuration-interaction method in complete active space. The calculated results are in excellent agreement with experimental measurements. The potential energy curves at numerous basis sets for this state are obtained over a wide internuclear separation range from about 2.4a0 to 37.0a0. And the conclusion is gained that the basis set 6-311＋＋G（d,p） is a most suitable one. The calculated spectroscopic constants De, Re, ωe, ωeχe, ae and Be at 6-311＋＋G（d,p） are 0.9670 eV, 0.3125 nm, 238.6 cm^-1, 1.3705 cm^-1, 0.0039 cm^-1 and 0.4921 cm^-1, respectively. The vibrational levels are calculated by solving the radial SchrSdinger equation of nuclear motion. A total of 53 vibrational levels are found and reported for the first time. The classical turning points have been computed. Comparing with the measurements, in which only the first nine vibrational levels have been obtained so far, the present calculations are very encouraging. A careful comparison of the present results of the parameters De and We with those obtained from previous theories clearly shows that the present calculations are much closer to the measurements than previous theoretical results, thus representing an improvement on the accuracy of the ab initio calculations of the potentials for this state.

Elastic and Optoelectronic Properties of KCdF3:ab initio Calculations through LDA/GGA/TB-mBJ within FP-LAPW Method

Ab initio calculations are performed on the electronic, structural, elastic and optical properties of the cubic per- ovskite KCdF3. Tile Kohn Sham equations are solved by applying the full potential linearized augmented plane wave （FP-LAPW） method. The exchange correlation effects are included through the local density approximation （LDA ）, generalized gradient approximation （GGA） and modified Becke-Johnson （mBJ） exchange potential The calculated lattice constant is in good agreement with the experimental result. The elastic properties such as elastic constants, anisotropy factor, shear modulus, Young＇s modulus and Poisson＇s ratio are calculated. KCdF3 is ductile and elastically anisotropic. The calculations of the electronic band structure, density of states （DOS） and charge density show that this compound has an indirect energy band gap （M-F） with a mixed ionic and covalent bonding. The contribution of the different bands is analyzed from the total and partial density of states curves. Optical response of the dielectric functions, optical reflectivity, absorption coefficient, real part of optical conductivity, refractive index, extinction coefficient and electron energy loss, are presented for the energy range of O-40eV. The compound KCdF3 can be used for high-frequency optical and optoelectronic devices.

One-colour resonant two-photon ionization spectrum of the 1-fluoronaphthalene dimer and ab initio calculation

The one-colour resonant two-photon ionization （R2PI） spectrum of the 1-fluoronaphthalene （1FN） dimer has been studied in the wavelength range of 304 to 322 nm by using a supersonic molecular beam and time-of-flight mass spectrometry. Compared with the original band 00^0 （at 313.8 nm） of the S1 ← So transition of the 1FN monomer, a red-shifted band was observed in the 1FN dimer spectrum at about 315 nm with a relatively large linewidth, nearly 2 nm. Based on the consideration of inductive effect and ab initio calculations, this red-shifted band is assigned to the first electronic excited transition of the 1FN dimer. A possible geometric structure of the 1FN dimer is also obtained with calculations that the two 1FN molecules are combined through two hydrogen bonds which are formed between the hydrogen atom of a molecule and the fluorine atom of a neighbouring molecule. A time-dependent calculation was also carried out and the results are consistent with the experimental data.

OPTIMAL SCHEME FOR SEQUENTIAL COMPUTATIONS OF F_m(z) INTEGRALS IN AB INITIO CALCULATIONS----COMBINATORY USE OF UPWARD AND DOWNWARD RECURSIONS

The quantitative rules of the transfer and variation of errors,when the Gaussian integral functions F.(z) are evaluated sequentially by recurring,have been expounded.The traditional viewpoint to negate the applicability and reliability of upward recursive formula in principle is amended.An optimal scheme of upward-and downward-joint recursions has been developed for the sequential F(z) computations.No additional accuracy is needed with the fundamental term of recursion because the absolute error of Fn(z) always decreases with the recursive approach.The scheme can be employed in modifying any of existent subprograms for Fn<z> computations.In the case of p-d-f-and g-type Gaussians,combining this method with Schaad's formulas can reduce,at least,the additive operations by a factor 40%;the multiplicative and exponential operations by a factor 60%.

Using Raman Spectroscopy and ab initio Calculations to Investigate Intermolecular Hydrogen Bonds in Binary Mixture (Tetrahydrofuran+Water)

We analyzed the properties and structures of the hydrogen-bonded complexes of tetrahydrofuran（THF） and water by means of experimental Raman spectra and ab initio calculations.The optimized geometries and vibrational frequencies of the neat THF molecule and its hydrogen-bonded complexes with water（THF/H2O） were calculated at the MP2/6-311＋G（d,p） level of theory.We found that the intermolecular hydrogen bonds which are formed from the binary mixtures of the neat THF and water with different molar ratios could explain the changes in wavenumber position and linewidth very well.The combination of ab initio calculations and experimental Raman spectral data provides an insight into the hydrogen bonds leading to the concentration dependent changes in the spectral features.

AB INITIO CALCULATION OF THE ELASTIC AND OPTICAL PROPERTIES OF Al3Sc COMPOUND

The ab initio method has been performed to explore the elastic and optical properties of Al3Sc compound, based on a plane wave pseudopotential method. It can be seen that the calculated equilibrium lattice parameter and elastic constants are in reasonable agreement with the previous experimental data. The elastic constants satisfy the requirement for mechanical stability in the cubic structure of the Al3Sc compound. The optical property calculations show that a strong absorptive peak exists from O-15eV and a relative small absorptive peak exists around 30eV. The form is caused by the optical transitions between high s, p, and d bands, and the latter results from the optical transitions from high s, p, and d bands to the low 2p band.

Ab Initio Calculation of Dielectric Function in Wurtzite GaN Based on Walter's Model

The wavelength-dependent and frequency-dependent dielectric function of wurtzite-GaN is cMculated totally from fundamental parameters such as the lattice constant using Waiter＇s ab initio model. The errors occurring in the cMculation are carefully reduced by/inear interpolation of energy data. The Kramers-Kronig transform of the real part of greater range is obtained by extrapolation of the reM part. The calculation is time-consuming but meaningful The long-wave results are similar to the experimental data of the photon and are useful for related investigation of properties of wide-gap semiconductors such as electron scattering like the Auger recombination and impact ionization.

A NEW AB INITIO CALCULATION METHOD OF INNER-SPHERE REORGANIZATION ENERGY

On the basis of the-improved self-exchange model of reorganization phenomenon and accurate potential functions from ab initio calculation at HFSCF 6-31G* and DZP levels a new calculation method was,presented for the inner-sphere reorganization energy, values for diatomic molecular redox couples in gas phase electron transfer process have been calculated. Results agree well with the experimental data, and the effectiveness and importance of this method have been demonstrated for calculation of inner-sphere reorganization energy in gas phase electron transfer process.

Ab Initio Calculation of the Electronic States of ScTe Molecule below 19,500 cm-1

The potential energy curves (PECs) of the16 lowest electronic states in the representation 2s+1Λ (+/-) of the molecule ScTe have been investigated via ab initio CASSCF and MRCI (single and double excitations with Davidson correction) calculations. The permanent dipole moment curves (PDMCs) and the spectroscopic constants such as vibrational harmonic frequency ωe, the internuclear distance at equilibrium Re, the rotational constant Be, and the electronic transition energy Te with respect to the ground state have been calculated for the different bound investigated electronic states. The comparison of the present results with the rare available theoretical data in literature shows an overall good agreement. To the best of our knowledge, 15 electronic states of the ScTe molecule are not yet investigated either experimentally or theoretically, they are investigated in the present work for the first time.

Ground-state mass of ^(22)Al and test of state-of-the-art ab initio calculations

The ground-state mass excess of the T_(z)=−2 drip-line nucleus ^(22)Al is measured for the first time as 18103(10)keV using the newly-developed Bρ-defined isochronous mass spectrometry method at the cooler storage ring in Lanzhou.The new mass excess value allowed us to determine the excitation energies of the two low-lying 1+states in ^(22)Al with significantly reduced uncertainties of 51 keV.When compared to the analogue states in its mirror nucleus ^(22)F,the mirror energy differences of the two 1^(+)states in the ^(22)Al-^(22)F mirror pair are determined to be−625(51)keV and−330(51)keV.The excitation energies and mirror energy differences are used to test the state-of-the-art ab initio valence-space in-medium similarity renormalization group calculations with four sets of interactions derived from the chiral effective field theory.The mechanism leading to the large mirror energy differences is investigated and attributed to the occupation of theπs_(1/2) orbital.

Identifying the crystal structure of T 1 precipitates in Al-Li-Cu alloys by ab initio calculations and HAADF-STEM imaging

Controversial experimental reports on the crystal structure of T 1 precipitates in Al-Li-Cu alloys have ex-isted for a long time,and all of them can be classified into five models.To clarify its ground-state atomic structure,herein,we have combined high-throughput first-principles calculations and CALPHAD,as well as aberration-corrected HAADF-STEM experiments.Employing the special quasi-random structure(SQS)and supercell approximation(SPA)methods to simulate the local disorder on Al-Cu sub-lattices,we find that none of the present models can satisfy the phase stability in Al-Li-Cu ternary system based on temperature-dependent convex hull analysis.Using the cluster expansion(CE)formulas,structural predic-tions derived from the five-frame models were performed.Subsequently,by introducing the vibrational contribution to the free energy at aging temperatures,we proposed a novel ground-state T 1 structure that maintains a coherent relationship with Al-matrix at the<112>Al orientation.The underlying phase transition between the variants of T 1 precipitates was further discussed.By means of ab initio molecular dynamics(AIMD)simulations,we resolved the controversy regarding the number of atomic layers con-stituting the T 1 phase and acknowledged the existence of Al-Li corrugated layers.The root cause of this structural distortion is triggered by atomic forces and bondings.Our work can have an positive impact on the novel fourth generation of Al-Cu-Li alloy designs by engineering the T 1 strengthening phase.

Ab initio calculations on accurate dissociation energy, equilibrium geometry, and analytic potential energy function for the 6~3Π state of ~7LiH molecule

The accurate dissociation energy and equilibrium geometry of the ball state of ^7LiH molecule is calculated using a symmetry-adapted-cluster configuration-interaction method in full active space. And the calculated results are 0.2580 eV and 0.1958 nm for the dissociation energy and equilibrium geometry, respectively. The whole potential energy curve for the b^3∏ state is also calculated over the internuclear separation range from about 0.10 to 0.54 nm. The results are fitted by the Murrell-Sorbie function. It is found that the Murrell-Sorbie function form, which is mainly used to fit the ground-state potential energy function, is well suitable for the excited triplet b^3∏ state. The vertical excitation energy from the ground state to the b^3∏ state is calculated to be 4.233 eV. Based on the analytic potential energy function, the harmonic frequency of 610.88 cm^-1 about this state is firstly estimated. Compared with other theoretical results, this work is the most complete effort to deal with the analytic potential energy function and the harmonic frequency of this state.

Rotational Isomeric State Model of Poly(vinylidene chloride) Based Upon ab Initio Electronic Structure Calculations

The rotational isomeric state（RIS） model was constructed for poly（vinylidene chloride）（PVDC） based on quantum chemistry calculations. The statistical weighted parameters were obtained from RIS representations and ab initio energies of conformers for model molecules 2,2,4,4-tetrachloropentane（TCP） and 2,2,4,4,6, 6-hexachloroheptane（HCH）. By employing the RIS method, the characteristic ratio C∞ was calculated for PVDC. The calculated characteristic ratio for PVDC is in good agreement with experiment result. Additionally, we studied the influence of the statistical weighted parameters on C∞ by calculating δC∞/δlnw. According to the values of δC∞/δlnw, the effects of second-order Cl-CH2 pentane type interaction and C1--C1 long range interaction on C∞ were found to be important. In contrast, first-order interaction is unimportant.

Studies on nitramide and its methyl derivatives with ab initio calculations——Ⅳ.The harmonic force field and vibrational spectra of dimethylnitramine and its isotopic derivatives

The complete harmonic vibrational force field of dimethylnitramine has been calculated at the Hartree-Fock level using 4-21G basis set.The harmonic force field was then scaled with scale factors previously derived from N-methylnitramine,and the vibrational spectrum of dimethylnitramine was computed.This apriori prediction,made with no reference to observations on dimethylnitramine, agrees with the experimental IR spectrum in gas phase with a mean deviation of 8.4 cm^(-1).Some of the scale factors were reoptimized by fitting of the computed force field to experimental data.The new set of scale factors reduced the mean deviation to 4.5 cm^(-1),and was used to predict the vibrational spectrum of deuterated form of dimethylnitramine(-6D).Dipole moment derivatives were also cal- culated and used to predict infrared intensities which are comparable with experimental values.