Density functional study on chirospectra of hydrogen-bonded systems X-（H2O）3（X=F,Cl,Br,I）

This paper calculates the molecular structures,infrared,Raman,circular dichroism spectra and optical rotatory powers of some hydrogen-bonded supramolecular systems as a cyclic water trimer,(H2O)3 and its pyramidal halide complexes,X-(H2O)3(X = F,Cl,Br,I) with the gradient-corrected density functional theory method at the B3LYP/6-311++G(2d,2p) and B3LYP/Aug-cc-pVTZ levels.It finds that the complexation of halide anions with the water trimer can efficiently modulate the chirally optical behaviors.The calculated vibrational circular dichroism spectrum illuminates that the vibrational rotational strength of S(+)-(H2O)3 mostly originates from the O-H rocking modes,whereas chirality of S(-)-X-(H2O)3(X = F,Cl,Br,I) has its important origin in the O-H stretching modes.The calculated optical rotatory power demonstrates that S(+)-(H2O)3 and S(+)-F(H2O)3 are positively chiral,whereas S(-)-X-(H2O)3(X = Cl,Br,I) are negatively chiral.With the polarizable continuum model,calculated bulk solvent effect in the solvents water and carbontetrachloride and argon shows that the positive chirality of S(+)-(H2O)3 is enhanced and the negative chirality of S(-)-X-(H2O)3(X = Cl,Br,I) and the positive chirality of S(+)-F(H2O)3 are reduced with an augmentation of the solvent dielectric constant.     

A new analysis of the ν2 fundamental band of H2O^＋＊

This paper reports that the absorption spectra of H2O^＋ have been measured by tunable mid-infrared diode laser spectroscopy in the spectral range of 1100-1380 cm^-1. The H2O＋ ions are generated in an AC glow discharge of the gaseous mixtures of H2O/He and detected with the velocity modulation technique. Forty new lines are assigned to the ν2 fundamental band of H2O^＋ （X^2B1）. The observed lines together with other data published previously are fitted to the standard effective Hamiltonian of an asymmetric top, yielding a set of improved rotational constants, spin-rotation constants and their quartic and sextic centrifugal distortion constants for the ν2=1 vibrational state of H2O＋.     

溶胶凝胶法制备参氟二氧化锡薄膜

利用溶胶凝胶方法，在硅碱玻璃底板上制备的透明低电阻SnO2:F薄膜，是一种低辐射导电薄膜。将SnCl4·5H2O 和 NH4F 溶解在50%乙醇和50%水的溶液中。制备条件为底板温度450℃，喷嘴与底板之间的距离60mm,载气流速8 L/min，制备时间5分钟。制成的SnO2:F薄膜面电阻为2Ω/□，可重复性好。并且文中还定性给出了SnO2:F薄膜其红外反射率与面电阻之间的关系。     

Characterization of PolyA and PolyC mismatches by Raman spectroscopy

A.C mismatches are studied by Raman spectral characterization of PolyA, PolyC, and their equimolar complex in solution of 0.14 mol/L Na ,pH7.0.Experimental results show that A·C mismatches occur to be A/B (mainly A) conformers, and unlike Watson-Crick base pairing, this kind of mismatches is stabilized by only one hydrogen bond involving cytosine N4H2 and adenine N7.The formation of A·C complex makes the base stacking interactions much stronger, and conformation of the backbone more ordered, which leads to obvious Raman hypochromic effect with some shifts in corresponding bands.     

Structural evolution and molecular dissociation of H2S under high pressures

Solid H$_{2}$S as the precursor for H$_{3}$S with incredible superconducting properties under high pressure, has recently attracted extensive attention. Here in this work, we propose two new phases of H$_{2}$S with $P$4$_{2}/n$ and $I$4$_{1}/a$ lattice symmetries in a pressure range of 0 GPa-30 GPa through first-principles structural searches, which complement the phase transition sequence. Further an $ab initio$ molecular dynamics simulation confirms that the molecular phase $P2/c$ of H$_{2}$S is gradually dissociated with the pressure increasing and reconstructs into a new $P$2$_{1}/m$ structure at 160 GPa, exhibiting the superconductivity with $T_{\rm c}$ of 82.5 K. Our results may provide a guidance for the theoretical study of low-temperature superconducting phase of H$_{2}$S.     

Analysis of Dα（Hα） spectrum emitted in front of the limiter in HT-7^＊

In order to understand the recycling and emission processes of hydrogen atoms in HT 7, spectral profiles of the Dα（Hα） line emitted in front of the limiter have been observed with a high-resolution spectrometer and simulated by using the neutral particle transport code DEGAS 2. The results show that four processes are necessary to interpret the Dα（Hα） line shape： 1） atom desorption, 2） molecular dissociation, 3） particle reflection, and 4） charge-exchange. The products of the first two processes are cold atoms which emit photons near the peak of Dα（Hα） line shape, and those from the last two are warm atoms contributing to the blue side of the spectrum. For a typical ohmic discharge （shot 68520 ne（0） ≈ 3× 10^19 m^-3. these components contribute 32%, 15%, 32% and 21%, respectively. Dα（Hα） line shapes under different plasma parameters are also discussed in this paper.     

Nanosecond-time-resolved infrared spectroscopic study of fast relaxation kinetics of protein folding by means of laser-induced temperature-jump

Elucidating the initial kinetics of folding pathways is critical to the understanding of the protein folding mechanism. Transient infrared spectroscopy has proved a powerful tool to probe the folding kinetics. Herein we report the construction of a nanosecond laser-induced temperature-jump （T-jump） technique coupled to a nanosecond timeresolved transient mid-infrared （mid-IR） spectrometer system capable of investigating the protein folding kinetics with a temporal resolution of 50 ns after deconvolution of the instrumental response function. The mid-IR source is a liquid N2 cooled CO laser covering a spectral range of 5.0μm （2000 cm^-1）-6.5μm （1540 cm^-1）. The heating pulse was generated by a high pressure H2 Raman shifter at wavelength of 1.9μm. The maximum temperature-jump could reach as high as 26±1℃. The fast folding/unfolding dynamics of cytochrome C was investigated by the constructed system, providing an example.     

Ground state for CH2 and symmetry for methane decomposition

Using the different level of methods B3P86, BLYP, B3PW91, HF, QCISD、 CASSCF （4,4） and MP2 with the various basis functions 6-311G^＊＊, D95, cc-pVTZ and DGDZVP, the calculations of this paper confirm that the ground state is X^-3B1 with C2v group for CH2. Furthermore, the three kinds of theoretical methods, i.e. B3P86、 CCSD（T, MP4） and G2 with the same basis set cc-pVTZ only are used to recalculate the zero-point energy revision which are modified by scaling factor 0.989 for the high level based on the virial theorem, and also with the correction for basis set superposition error. These results are also contrary to X^-3∑^-g for the ground state of CH2 in reference. Based on the atomic and molecular reaction statics, this paper proves that the decomposition type （1） i.e. CH4 →CH2＋H2, is forbidden and the decomposition type （2） i.e. CH4→CHa＋H is allowed for CH4. This is similar to the decomposition of SiH4.     

The role of hydrogen in hydrogenated microcrystalline silicon film and in deposition process with VHF-PECVD technique

The role of hydrogen in hydrogenated microcrystalline silicon ($\mu $c-Si:H) thin films in deposition processes with very high frequency plasma-enhanced chemical vapour deposition (VHF-PECVD) technique have been investigated in this paper. With \textit{in situ} optical emission spectroscopy (OES) diagnosis during the fabrication of $\mu $c-Si:H thin films under different plasma excitation frequency $\nu _{\rm e }$ (60MHz--90MHz), the characteristic peak intensities ($I_{{\rm SiH}^*}$, $I_{{\rm H}\alpha^*}$ and $I_{{\rm H}\beta ^*}$) in SiHVHF-PECVD技术 氢化微晶硅 光发射光谱 薄膜学VHF-PECVD technique, hydrogenated microcrystalline silicon, role of hydrogen, optical emission spectroscopyProject supported by the Natural Science Foundation of Guangdong Province, China (Grant No 05300378), the State Key Development Program for Basic Research of China (Grant Nos G2000028202 and G2000028203) and the Program on Natural Science of Jinan University, Guangzhou, China (Grant No 51204056).2005-11-252005-11-252006-01-05The role of hydrogen in hydrogenated microcrystalline silicon （μc-Si：H） thin films in deposition processes with very high frequency plasma-enhanced chemical vapour deposition （VHF-PECVD） technique have been investigated in this paper. With in situ optical emission spectroscopy （OES） diagnosis during the fabrication of μc-Si：H thin films under different plasma excitation frequency Ve （60MHz-90MHz）, the characteristic peak intensities （IsiH＊, IHα＊ and IHβ＊ ） in SiH4＋H2 plasma and the ratio of （IHα＊ ＋ IHβ＊ ） to IsiH＊ were measured; all the characteristic peak intensities and the ratio （IHα＊ ＋ IHβ＊ ）/IsiH＊ are increased with plasma excitation frequency. It is identified that high plasma excitation frequency is favourable to promote the decomposition of SiH4＋H2 to produce atomic hydrogen and SiHx radicals. The influences of atomic hydrogen on structural properties and that of SiHx radicals on deposition rate of μc-Si：H thin films have been studied through Raman spectra and thickness measurements, respectively. It can be concluded that both the crystalline volume fraction and deposition rate are enhanced with the increase of plasma excitation frequency, which is in good accord with the OES results. By means of FTIR measurements, hydrogen contents of μc-Si：H thin films deposited at different plasma excitation frequency have been evaluated from the integrated intensity of wagging mode near 640 cm^-1. The hydrogen contents vary from 4% to 5%, which are much lower than those of μc-Si：H films deposited with RF-PECVD technique. This implies that μc-Si：H thin films deposited with VHF-PECVD technique usually have good stability under light-soaking.     

High density gas state at water/graphite interface studied by molecular dynamics simulation

In this paper molecular dynamics simulations are performed to study the accumulation behaviour of N2 and H2 at water/graphite interface under ambient temperature and pressure. It finds that both N2 and H2 molecules can accumulate at the interface and form one of two states according to the ratio of gas molecules number to square of graphite surface from our simulation results： gas films （pancake-like） for a larger ratio and nanobubbles for a smaller ratio. In addition, we discuss the stabilities of nanobubbles at different environment temperatures. Surprisingly, it is found that the density of both kinds of gas states can be greatly increased, even comparable with that of the liquid N2 and liquid H2. The present results are expected to be helpful for the understanding of the stable existence of gas film （pancake-like） and nanobubbles.     

Calculations of state-selective differential cross sections for charge transfer in collisions between O3+ and H2

The non-dissociative charge-transfer processes in collisions between O^3＋ and H2 are investigated by using the quantum-mechanical molecular-orbital coupled-channel （QMOCC） method. The adiabatic potentials and radial coupling matrix elements utilized in the QMOCC calculations are obtained with the spin-coupled valence-bond approach. Electronic and vibrational state-selective differential cross sections are presented for projectile energies of 0.1, 1.0 and 10.0eV/u in the H2 orientation angles of 45° and 89°. The electronic and the vibrational state-selective differential cross sections show similar behaviours： they decrease as the scattering angle increases, and beyond a specific angle the oscillating structures appear. Moreover, it is also found that the vibrational state-selective differential cross sections are strongly orientation-dependent, which provides a possibility to determine the orientations of molecule H2 by identifying the vibrational state-selective differential scattering processes.     

Improved performance of MoS2 FET by in situ NH3 doping in ALD Al2O3 dielectric

Since defects such as traps and oxygen vacancies exist in dielectrics, it is difficult to fabricate a high-performance MoS$_{2}$ field-effect transistor (FET) using atomic layer deposition (ALD) Al$_{2}$O$_{3}$ as the gate dielectric layer. In this paper, NH$_{3}$ in situ doping, a process treatment approach during ALD growth of Al$_{2}$O$_{3}$, is used to decrease these defects for better device characteristics. MoS$_{2}$ FET has been well fabricated with this technique and the effect of different NH$_{3}$ in situ doping sequences in the growth cycle has been investigated in detail. Compared with counterparts, those devices with NH$_{3}$ in situ doping demonstrate obvious performance enhancements: $I_{\rm on}/I_{\rm off}$ is improved by one order of magnitude, from $1.33\times 10^{5}$ to $3.56\times 10^{6}$, the threshold voltage shifts from $-0.74 $ V to $-0.12$ V and a small subthreshold swing of 105 mV/dec is achieved. The improved MoS$_{2}$ FET performance is attributed to nitrogen doping by the introduction of NH$_{3}$ during the Al$_{2}$O$_{3}$ ALD growth process, which leads to a reduction in the surface roughness of the dielectric layer and the repair of oxygen vacancies in the Al$_{2}$O$_{3}$ layer. Furthermore, the MoS$_{2}$ FET processed by in situ NH$_{3}$ doping after the Al and O precursor filling cycles demonstrates the best performance; this may be because the final NH$_{3}$ doping after film growth restores more oxygen vacancies to screen more charge scattering in the MoS$_{2}$ channel. The reported method provides a promising way to reduce charge scattering in carrier transport for high-performance MoS$_{2 }$ devices.     

The evaluation of bond dissociation energies for NO2 scission in nitro compounds using density functional and complete basis set methods

By using the density functional theory （B3LYP） and four highly accurate complete basis set （CBS-Q, CBS-QB3, CBS-Lq, and CBS-4M）ab initio methods, the X（C, N, O）-NO2 bond dissociation energies （BDEs） for CH3NO2, C2H3NO2, C2H5NO2, HONO2, CH3ONO2, C2H5ONO2, NH2NO2 （CH3）2NNO2 are computed. By comparing the computed BDEs and experimental results, it is found that the B3LYP method is unable to predict satisfactorily the results of bond dissociation energy （BDE）; however, all four CBS models are generally able to give reliable predication of the X（C, N, O）-NO2 BDEs for these nitro compounds. Moreover, the CBS-4M calculation is the least computationally demanding among the four CBS methods considered, Therefore, we recommend CBS-4M method as a reliable method of computing the BDEs for this nitro compound system.     

Optical spectroscopy study of damage evolution in 6H-SiC by H_2~+ implantation

Lattice defects induced by ion implantation into Si C have been widely investigated in the decades by various techniques. One of the non-destructive techniques suitable to study the lattice defects in Si C is the optical characterization. In this work, confocal Raman scattering spectroscopy and photoluminescence spectrum have been used to study the effects of 134-ke V H_2~+ implantation and thermal treatment in the microstructure of 6 H-Si C single crystal. The radiation-induced changes in the microstructure were assessed by integrating Raman-scattering peaks intensity and considering the asymmetry of Raman-scattering peaks. The integrated intensities of Raman scattering spectroscopy and photoluminescence spectrum decrease with increasing the fluence. The recovery of the optical intensities depends on the combination of the implantation temperature and the annealing temperature with the thermal treatment from 700℃ to 1100℃. The different characterizations of Raman scattering spectroscopy and photoluminescence spectrum are compared and discussed in this study.     

Studies of diamond-like carbon （DLC） films deposited on stainless steel substrate with Si/SiC intermediate layers

In this work, diamond-like carbon （DLC） films were deposited on stainless steel substrates with Si/SiC intermediate layers by combining plasma enhanced sputtering physical vapour deposition （PEUMS-PVD） and microwave electron cyclotron resonance plasma enhanced chemical vapour deposition （MW-ECRPECVD） techniques. The influence of substrate negative self-bias voltage and Si target power on the structure and nano-mechanical behaviour of the DLC films were investigated by Raman spectroscopy, nano-indentation, and the film structural morphology by atomic force microscopy （AFM）. With the increase of deposition bias voltage, the G band shifted to higher wave-number and the integrated intensity ratio ID/IG increased. We considered these as evidences for the development of graphitization in the films. As the substrate negative self-bias voltage increased, particle bombardment function was enhanced and the sp^3-bond carbon density reducing, resulted in the peak values of hardness （H） and elastic modulus （E）. Silicon addition promoted the formation of sp^3 bonding and reduced the hardness. The incorporated Si atoms substituted sp^2- bond carbon atoms in ring structures, which promoted the formation of sp^3-bond. The structural transition from C-C to C-Si bonds resulted in relaxation of the residual stress which led to the decrease of internal stress and hardness. The results of AFM indicated that the films was dense and homogeneous, the roughness of the films was decreased due to the increase of substrate negative self-bias voltage and the Si target power.     

GaN layers with different polarities prepared by radio frequency molecular beam epitaxy and characterized by Raman scattering

GaN layers with different polarities have been prepared by radio-frequency molecular beam epitaxy (RF-MBE) and characterized by Raman scattering. Polarity control are realized by controlling Al/N flux ratio during high temperature AlN buffer growth. The Raman results illustrate that the N-polarity GaN films have frequency shifts at $A_{1}$(LO) mode because of their high carrier density; the forbidden $A_{1}$(TO) mode occurs for mixed-polarity GaN films due to the destroyed translation symmetry by inversion domain boundaries (IDBS); Raman spectra for Ga-polarity GaN films show that they have neither frequency shifts mode nor forbidden mode. These results indicate that Ga-polarity GaN films have a better quality, and they are in good agreement with the results obtained from the room temperature Hall mobility. The best values of Ga-polarity GaN films are 1042 cm$^{2}$/Vs with a carrier density of 1.0$\times $10$^{17}$~cm$^{ - 3}$.     

高速H2+离子轰击C靶诱发二次电子的发射行为与入射角的关系

运用Monte-Carlo方法结合半经验理论研究了高速H2+离子轰击C靶诱发二次电子的发射行为与入射角的关系。分别研究了电子发射产额与入射角以及发射统计性与入射角的关系。结果表明，由于H2+上的价电子的影响使得背向电子发射产额不遵守余弦倒数关系。斜入射时候的前向与背向电子产额的比值跟正入射时的情况不同。电子的发射统计跟入射角没有关系。标志偏离Poission分布的值 b，随入射能量的增加而增大。     

Intermolecular H‐bond in propan‐2‐ol and its solutions with acetonitrile

Formation of propan‐2‐ol–acetonitrile dimers is manifested in the Raman spectra as an appearance of a band of aggregates in the high‐wavenumber side of the CN vibrational band of liquid acetonitrile (∼2 cm⁻¹). The intensity of the band of aggregates changes with a change in the concentration of the mixture (1–0.05 mole fraction). For propan‐2‐ol we carried out nonempirical calculations of a structure of isolated dimer aggregates. The formation of an intramolecular H‐bond between the H and the O atom of the \newbox\osprulebox \newdimen\osprulewd \def\osprule#1#2{ \global\setbox\osprulebox=\hbox{#1} \osprulewd=\wd\osprulebox\advance\osprulewd by ‐8pt \raise0.5pc\hbox{$\matrix{\hskip‐1pt\lower6.5pt\hbox{\vrule height #2pt}\lower4.5pt\hbox to \osprulewd{\hrulefill}\lower6.5pt\hbox{\vrule height #2pt}\cr \noalign{\vskip‐1pt} \hbox{#1}\cr}$} } $\osprule{{\rm HCO}}{2.5} \hbox{H}$ group of length 2.045 Å is possible in the monomer molecule. The CH₃ groups of alcohol are not equivalent. In the dimer formation, intramolecular H‐bond in the \newbox\osprulebox \newdimen\osprulewd \def\osprule#1#2{ \global\setbox\osprulebox=\hbox{#1} \osprulewd=\wd\osprulebox\advance\osprulewd by ‐8pt \raise0.5pc\hbox{$\matrix{\hskip‐1pt\lower6.5pt\hbox{\vrule height #2pt}\lower4.5pt\hbox to \osprulewd{\hrulefill}\lower6.5pt\hbox{\vrule height #2pt}\cr \noalign{\vskip‐1pt} \hbox{#1}\cr}$} } $\osprule{{\rm HCO}}{2.5} \hbox{H}$ group is preserved. An intermolecular H‐bond of length 2.045 Å and energy 15 kJ/mole is formed between the H atom of one molecule and the O atom of another molecule of the O H. The length and energy of the H‐bond for the propan‐2‐ol–acetonitrile dimer formations calculate to 2.27 Å and 12.9 kJ/mole, respectively. The H‐bond is formed by σ‐electrons of nitrogen. The experimental data and the results of calculations are in good agreement. Copyright © 2007 John Wiley & Sons, Ltd.     

Ab initio calculations on the α^3∑u^＋ state properties of dimer ^7Li2

The comparison between single-point energy scanning （SPES） and geometry optimization （OPT） in determining the equilibrium geometry of the α^3∑u^＋ state for ^7Li2 is made at numerous basis sets such as 6-311＋＋G（2df）, cc-PVTZ, 6-311＋＋G（2df, p）, 6-311G（3df,3pd）, 6-311＋＋G（2df,2pd）, D95（3df,3pd）, 6-311＋＋G, DGDZVP, 6-311＋＋G（3df,2pd）, 6-311G（2df,2pd）, D95V＋＋, CEP-121G, 6-311＋＋G（d,p）, 6-311＋＋G（2df, pd） and 6-311＋＋G（3df,3pd） in full active space using a symmetry-adapted-cluster/ symmetry-adapted-cluster configuration-interaction （SAC/SAC=CI） method presented in Gaussian03 program package. The difference of the equilibrium geometries obtained by SPES and by OPT is reported. Analyses show that the results obtained by SPES are more reasonable than those obtained by OPT. We have calculated the complete potential energy curves at those sets over a wide internuclear distance range from about 3.0α0 to 37.0α0, and the conclusion is that the basis set cc-PVTZ is the most suitable one. With the potential obtained at ccopVTZ, the spectroscopic data （Te, De, D0, ωe,ωeХe, αe and Be） are computed and they are 1.006 eV, 338.71 cm^-1, 307.12 cm^-1, 64.88 cm^-1, 3.41 cm^-1, 0.0187 cm^-1 and 0.279 cm^-1, respectively, which are in good agreement with recent measurements. The total 11 vibrational states are found at J=0. Their corresponding vibrational levels and classical turning points are computed and compared with available RKR data, and good agreement is found. One inertial rotation constant （By） and six centrifugal distortion constants （Dr Hv, Lv, My, Nv, and Ov） are calculated. The scattering length is calculated to be -27.138α0, which is in good accord with the experimental data.     

Incommensurate-commensurate magnetic phase transition in double tungstate Li2Co(WO4)2

Magnetic susceptibility, specific heat, and neutron powder diffraction measurements have been performed on polycrystalline Li$_{2}$Co(WO$_{4}$)$_{2}$ samples. Under zero magnetic field, two successive magnetic transitions at $T_{\rm N1}\sim 9.4$ K and $T_{\rm N2}\sim 7.4$ K are observed. The magnetic ordering temperatures gradually decrease as the magnetic field increases. Neutron diffraction reveals that Li$_{2}$Co(WO$_{4}$)$_{2}$ enters an incommensurate magnetic state with a temperature dependent $\bm k$ between $T_{\rm N1}$ and $T_{\rm N2}$. The magnetic propagation vector locks-in to a commensurate value $\bm k = (1/2, 1/4, 1/4)$ below $T_{\rm N2}$. The antiferromagnetic structure is refined at 1.7 K with Co$^{2+}$ magnetic moment 2.8(1) $\mu_{\rm B}$, consistent with our first-principles calculations.