Extended Measurement of the v2 (1- ←0+) Band of H3O+ by Mid-Infrared Diode Laser Spectroscopy

Twenty-five new R-branch lines of the v2（1^-← 0^＋） band of H3O^＋ are measured using diode laser velocity modulation spectroscopy between 1070 and 1230 cm^-1. The H3O^＋ ions are produced in a high voltage ac discharge with water diluted in helium. The observed lines together with all the previously published measurements are fit to the standard vibration-rotational Hamiltonian of an oblate symmetric top, yielding a set of improved molecular constants. All the sextic centrifugal distortion constants for both 0^＋ and 1^- states are determined precisely. The observed R（13, 0） transition is shifted about -0.129 cm^-1 from its calculated value, indicating that a near degeneracy exists between the （13, 0）^＋ and （13, 3）^- ground-state rotation-inversion levels.     

Infrared diode laser spectroscopy of O2–N2O van der Waals complex in the v1 symmetric stretch region of N2O

The rovibrational spectrum of O2–N2O van der Waals complex is measured in the ν1 symmetric stretch region of N2 O monomer using a tunable diode laser spectrometer. The complex is generated by a slit-pulsed supersonic expansion with gas mixtures of O2, N2 O, and He. Both a- and b-type transitions are observed. The effective Hamiltonian for an open-shell complex consisting of a diatomic molecule in a ^3Σ electronic state and a closed-shell partner is used to analyze the observed spectrum. Molecular constants in the vibrationally excited state are determined accurately. The band-origin of the spectrum is determined to be 1284.7504（25） cm^-1, red-shifted from that of the N2 O monomer by ～ 0.1529 cm^-1.     

Absolute Cross Sections for Near-Threshold Electron-Impact Excitation of the 2s^2S→2p^2P Transition of Li-Like C^3＋, N^4＋, and O^5＋ Ions

Excitation cross sections of 1s^22s ^2S1/2 → 1s^22p^2p1/2,3/2 transition among the fine-structure levels in Li-like C^3＋, N^4＋, and O^5＋ ions are calculated for energies of the near-threshold by using the relativistic distorted-wave program REIE06. The target state wavefunctions are calculated by using the Grasp92 code. The continuum orbitals are studied in the distorted-wave approximation, in which the direct and exchange potentials among all the electrons are included. The results of the Li-like C^3＋ ion settle the discrepancy between several previous experiments by using the crossed-beams fluorescence method, in good agreement with the measurements of Savin et al. Moreover, the results in Li-like N^4＋, and O^5＋ ions are compared with the previous experiments, and a good agreement is obtained.     

The structure and the analytical potential energy function of NH2 （X^2B1）

This paper reports that the equilibrium structure of NH2 has been optimized at the QCISD/6-311＋＋G （3df, 3pd） level. The ground-state NH2 has a bent （C2v, X^2B1） structure with an angle of 103.0582°. The geometrical structure is in good agreement with the other calculational and experimental results. The harmonic frequencies and the force constants have also been calculated. Based on the group theory and the principle of microscopic reversibility, the dissociation limits of NH2（C2v, X^2B1） have been derived. The potential energy surface of NH2（X^2B1） is reasonable. The contour lines are constructed, the structure and energy of NH2 reappear on the potential energy surface.     

Space-Selective Precipitation of Ba2TiSi2O8 Crystals in Sm3^＋-Doped BaO-TiO2-SiO2 Glass by Femtosecond Laser Irradiation

The ferroelectric crystal Ba2TiSi2O8 with high second-order optical nonlinearity is precipitated in Sm^3＋-doped BaO-TiO2-SiO2 glass by a focused 800hm, 250 kHz and 150fs femtosecond laser irradiation. No apparent blue and red emissions are observed at the beginning, while strong blue emission due to second harmonic generation and red emission due to the f-f transitions of Sm^3＋ are observed near the focal point of the laser beam after irradiation for 25s. Micro-Raman spectra confirm that Ba2 TiSi2O8 crystalline dots and lines are formed after laser irradiation. The mechanism of the phenomenon is discussed.     

The effect of an anti-hydrogen bond on Fermi resonance:A Raman spectroscopic study of the Fermi doublet ν1-ν12 of liquid pyridine

The effects of an anti-hydrogen bond on the ν1-ν12 Fermi resonance(FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy.Three systems,pyridine/water,pyridine/formamide,and pyridine/carbon tetrachloride,provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex.Water forms a stronger anti-hydrogen bond with pyridine than with formamide,and in the case of adding non-polar solvent carbon tetrachloride,which is neither a hydrogen bond donor nor an acceptor and incapable of forming a hydrogen bond with pyridine,the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce.The dilution studies are performed on the three systems.Comparing with the values of the Fermi coupling coefficient W of the ring breathing mode ν1 and triangle mode ν12 of pyridine at different volume concentrations,which are calculated according to the Bertran equations,in three systems,we find that the solution with the strongest anti-hydrogen bond,water,shows the fastest change in the ν1-ν12 Fermi coupling coefficient W with the volume concentration varying,followed by the formamide and carbon tetrachloride solutions.These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν1-ν12 FR of pyridine.According to the mechanism of the formation of an anti-hydrogen bond in the complexes and the FR theory,a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν1-ν12 FR of pyridine is given.     

Franck--Condon factors and r-Centroids for the A 1∑+u-X1∑+g Band System of 107,109Ag2: Comparison of the Observed and Calculated Absorption Band Strengths

Franck-Condon factors and r-centrolds for the, A^1 ∑^＋ u-X^1∑^＋ 9 band system of ^107,109Ag2 are computed using Morse and Rydberg-Klein-Rees potentials for both lower and upper electronic states. The differences between the two sets of results are typically in the third decimal place for transitions involving vibrational levels with ν＇ and ν＂ up to about 15. Somewhat larger deviations appear for higher vibrational levels, but both sets of results follow the same pattern, which is to match well with the relative absorption band strength distribution in our experimental spectrum. The relative absorption band strengths are calculated by assuming that the electronic transition moment has only a weak dependence on the internuclear distance r. Good agreement between our measured and calculated absorption band strength ratios is found, which provides an excellent test of the calculated Franck- Condon factors and relative absorption band strengths. The r-centrold value for the （ν＇ = 0, ν＂ = 0） band is found to be approximately equal to the average value of r＇ and r＇＇e , indicating that the potentials of both states are not significantly aaharmonic around their minimum regions.     

The analytical potential energy function of flue gas SO₂（X¹A₁）

The equilibrium structure of flue gas SO 2 is optimized using the density functional theory (DFT)/ B3P86 method and CC-PV5Z basis. The result shows that it has a bent (C2V ,X1A1) ground state structure with an angle of 119.1184 . The vibronic frequencies and the force constants are also calculated. Based on the principles of atomic and molecular reaction statics (AMRS), the possible electronic states and reasonable dissociation limits for the ground state of SO2 molecule are determined. The potential functions of SO and O2 are fitted by the modified Murrell–Sorbie+c6 (M-S+c6) potential function and the fitted parameters, the force constants and the spectroscopic constants are obtained, which are all close to the experimental values. The analytic potential energy function of the SO2 (X1A1) molecule is derived using the many-body expansion theory. The contour lines are constructed, which show the static properties of SO2 (X1A1), such as the equilibrium structure, the lowest energies, the most possible reaction channel, etc.     

Ab initio MRCI＋Q study on potential energy curves and spectroscopic parameters of low-lying electronic states of CS＋

Carbon monosulfide molecular ion （CS＋）, which plays an important role in various research fields, has long been attracting much interest. Because of the unstable and transient nature of CS＋, its electronic states have not been well investigated. In this paper, the electronic states of CS＋ are studied by employing the internally contracted multireference configuration interaction method, and taking into account relativistic effects （scalar plus spin–orbit coupling）. The spin–orbit coupling effects are considered via the state-interacting method with the full Breit–Pauli Hamiltonian. The potential energy curves of 18 Λ–S states correlated with the two lowest dissociation limits of CS＋ molecular ion are calculated, and those of 10 lowest Ω states generated from the 6 lowest Λ–S states are also worked out. The spectroscopic constants of the bound states are evaluated, and they are in good agreement with available experimental results and theoretical values. With the aid of analysis of Λ–S composition of Ω states at different bond lengths, the avoided crossing phenomena in the electronic states of CS＋ are illuminated. Finally, the single ionization spectra of CS （X1Σ＋） populating the CS＋（X2Σ1/2＋, A2Π3/2, A2Π1/2, and B2Σ1/2＋） states are simulated. The vertical ionization potentials for X2Σ1/2＋, A2Π3/2, A2Π1/2, and B2Σ1/2＋ states are calculated to be 11.257, 12.787, 12.827, and 15.860 eV, respectively, which are accurate compared with previous experimental results, within an error margin of 0.08 eV~0.2 eV.     

The analytical potential energy function of flue gas SO2（X1A1）

The equilibrium structure of flue gas SO2 is optimized using the density functional theory （DFT）/B3P86 method and CC-PV5Z basis. The result shows that it has a bent （C2v, X1A1） ground state structure with an angle of 119.1184°. The vibronic frequencies and the force constants are also calculated. Based on the principles of atomic and molecular reaction statics （AMIIS）, the possible electronic states and reasonable dissociation limits for the ground state of SO2 molecule are determined. The potential functions of SO and 02 are fitted by the modified Murrell-Sorbie＋c6 （M-S＋c6） potential function and the fitted parameters, the force constants and the spectroscopic constants are obtained, which are all close to the experimental values. The analytic potential energy function of the SO2 （X1A1） molecule is derived using the many-body expansion theory. The contour liues are constructed, which show the static properties of SO2 （XIA1）, such as the equilibrium structure, the lowest energies, the most possible reaction channel, etc.     

Improved Ligand-Field Theoretical Calculation of R-Line Pressure-Induced Shift of MgO：V^2＋

By means of an improved ligand-field theory, the ＂pure electronic＂ PS and the PS due to EPI of R line of MgO： V^2＋ have been calculated, respectively. The calculated results are in very good agreement with the experimental data. The behaviors of the pure electronic PS of R line of MgO：V^2＋ and the PS of its R line due to EPI are different. It is the combined effect of them that gives rise to the total PS of R line, which has satisfactorily explained the experimental results. The mixing-degree of ｜t2^2（^3T1）e^4T2〉 and ｜t2^3 ^2E〉 in the wavefunetion of R level and its variation with pressure have been calculated and analyzed. The comparison between the feature of R-line PS of MgO：V^2＋ and that of MgO：Cr^3＋ has been made.     

Isotopic Analysis to Determine All the Molecular Constants of O2^＋ in the A-X System

The linear correlated constants AD （centrifugal correction of the spin-orbit coupling constant） and γ （the spinrotation constant） involved in the second negative （A^2 Ⅱu-X^2 Ⅱg） system of O2^＋ are determined by nonlinear least-squares fitting the spectra of 16 O2^＋ and 18 0＋ using the isotopic effect. In addition, the molecular constants of the other O2^＋ isotopologues are predicted.     

The molecular structure and the analytical potential energy function of S2^- and S3^-

In this paper, the equilibrium geometry, harmonic frequency and dissociation energy of S2^- and S3^- have been calculated at QCISD/6-311＋＋G（3d2f） and B3P86/6-311＋＋G（3d2f） level. The S2^- ground state is of 2IIg, the S3^- ground state is of 2B1 and S3^- has a bent （C2v） structure with an angle of 115.65° The results are in good agreement with these reported in other literature. For S3^- ion, the vibration frequencies and the force constants have also been calculated. Base on the general principles of microscopic reversibility, the dissociation limits has been deduced. The Murrell-Sorbie potential energy function for S2^- has been derived according to the ab initio data through the least- squares fitting. The force constants and spectroscopic data for S2^- have been calculated, then compared with other theoretical data. The analytical potential energy function of S3^- have been obtained based on the many-body expansion theory. The structure and energy can correctly reappear on the potential surface.     

Effects of the vibrational and rotational excitation of reagent on the stereodynamics of the reaction S（3P） + H2→ SH + H

Quasiclassical trajectory （QCT） calculations are first carried out to study the stereodynamics of the S （3p） ＋ H2 → SH ＋ H reaction based on the ab initio 13Atr potential energy surface （PES） （Lii etal. 2012 J. Chem. Phys. 136 094308）. The QCT-calculated reaction probabilities and cross sections for the S ＋ H2 （v = 0, j = 0） reaction are in good agreement with the previous quantum mechanics （QM） results. The vector properties including the alignment, orientation, and polarization- dependent differential cross sections （PDDCSs） of the product SH are presented at a collision energy of 1.8 eV. The effects of the vibrational and rotational excitations of reagent on the stereodynamics are also investigated and discussed in the present work. The calculated QCT results indicate that the vibrational and rotational excitations of reagent play an important role in determining the stereodynamic properties of the title reaction.     

Phase transition and thermal expansion property of Cr_(2-x)Zr_(0.5x)Mg_(0.5x)Mo_3O_(12) solid solution

Compounds with the formula Cr2-xZr0.5xMg0.5xMo3O12（x = 0.0, 0.3, 0.5, 0.9, 1.3, 1.5, 1.7, 1.9） are synthesized, and the effects of Zr4＋ and Mg2＋ co-incorporation on the phase transition, thermal expansion, and Raman mode are investigated. It is found that Cr2-xZr0.5xMg0.5xMo3O12 crystallize into monoclinic structures for x 〈 1.3 and orthorhombic structures for x _〉 1.5 at room temperature. The phase transition temperature from a monoclinic to an orthorhombic structure of Cr2Mo3O12 can be reduced by the partial substitution of （ZrMg）6＋ for Cr3＋. The overall linear thermal expansion coefficient decreases with the increase of the （ZrMg）6＋ content in an orthorhombic structure sample. The co-incorporation of Zr4＋ and Mg2＋ in the lattice results in the occurrence of new Raman modes and the hardening of the symmetric vibrational modes, which are attributed to the MoO4 tetrahedra sharing comers with ZrO6/MgO6 octahedra and to the strengthening of Mo-O bonds due to less electronegativities of Zr4＋ and Mg2＋ than Cr3＋, respectively.     

First-Principles Calculation of Static Equation of State and Elastic Constants for GaSe

The all-electron full potential augmented plane-wave plus local orbital （APW_Io） method with the local-density approximation （LDA） is used to calculate the static equation of state （EOS） and elastic constants of crystalline GaSe. After the full relaxation of atomic positions, the calculated band structure at ambient pressure is consistent with the experimental data to the extent expected to give the known limits of LDA one-electron energies. The equilibrium lattice parameters found here exhibit the usual LDA-induced contraction. However, constrained with the experimental cell volume, the interlayer separation exhibits an expansion due to the LDA underestimate of the weak interlayer bonding. The calculated values of elastic constants are in good agreement with acoustic measurements. The pressure derivatives of the lattice constants derived from the theoretical elastic constants are in very good agreement with x-ray spectra measurements. Two analytical EOSs have been determined at pressures up to 4.5 GPa. The pressure evolution of the structure indicates that the layer thickness decreases slightly under pressure.     

Ab initio calculations on the spectroscopic constants, vibrational levels and classical turning points for the 21∏u 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.     

Luminescence and Energy Transfer of Eu^2＋, Mn^2＋ in SrZnP2O7

The SrZnP2OT：Eu^2＋, Mn^2＋ phosphor is synthesized by high temperature solid state reaction. The luminescence properties and the energy transfer between Eu^2＋ and Mn^2＋ are investigated. The emission bands of this phosphor peaked at 42Ohm and 67Ohm are originated from the 5d → 4f transition of Eu^2＋ and from the 4T1 （4G） --〉 6A1 （6S） transit/on of Mn^2＋, respectively. With the increasing Mn^2＋ concentration, the intensity of fixed concentra- tion Eu^2＋ decreases and the intensity of Mn^2＋ also increases. It is suggested that there is an energy transfer from Eu^2＋ to Mn^2＋ in SrZnP2O7 host. According to Dexter＇s energy transfer formula of multipolar interaction, the energy transfer between Eu^2＋ and Mn^2＋ is due to the electric dipole-quadrupole interaction of the resonance transfer.     

A density functional theory study on the adsorption of CO and O₂ on Cu-terminated Cu₂O（111） surface

The adsorptions of CO and O2 molecules individually on the stoichiometric Cu-terminated Cu2O(111) surface are investigated by first-principles calculations on the basis of the density functional theory.The calculated results indicate that the CO molecule preferably coordinates to the Cu2 site through its C atom with an adsorption energy of -1.69 eV,whereas the O2 molecule is most stably adsorbed in a tilt type with one O atom coordinating to the Cu2 site and the other O atom coordinating to the Cu1 site,and has an adsorption energy of -1.97 eV.From the analysis of density of states,it is observed that Cu 3d transfers electrons to 2π orbital of the CO molecule and the highest occupied 5σ orbital of the CO molecule transfers electrons to the substrate.The sharp band of Cu 4s is delocalized when compared to that before the CO molecule adsorption,and overlaps substantially with bands of the adsorbed CO molecule.There is a broadening of the 2π orbital of the O2 molecule because of its overlapping with the Cu 3d orbital,indicating that strong 3d-2π interactions are involved in the chemisorption of the O2 molecule on the surface.     

Comparison of Secondary Ion Emissions from Carbon Nanotubes under Bombardments of MeV Si and Si2 Clusters

The emission yields of H, H2, H3 and heavy ions from carbon nanotubes under bombardments of Si and Si2 clusters in an energy range of 0.3-3 MeV per atom are measured by using the time-of-flight technique (TOF). The emission yields of the secondary ions increase with increasing energy of Si and the electronic stopping processes play an important role. The enhanced emission yields of secondary ions induced by Si2 clusters at the low energies are clearly seen and attributed to the vicinage effect of the nuclear collision processes of cluster constituents and the secondary ion emissions are still dominated by electronic stopping processes at high energies.