异氰酸分子NH(a1Δ)+CO(X1Σ+)通道在193nm的离子成像光解动力学研究

The photodissociation dynamics of isocyanic acid (HNCO) has been studied by the timesliced velocity map ion imaging technique at 193 nm. The NH(a¹Δ) products were measured via (2+1) resonance enhanced multiphoton ionization. Images have been accumulated for the NH(a¹Δ) rotational states in the ground and vibrational excited state (v=0 and 1). The center-of-mass translational energy distribution derived from the NH(a¹Δ) images implies that the CO vibrational distributions are inverted for most of the measured ¹NH(v|j) internal states. The anisotropic product angular distribution observed indicates a rapid dissociation process for the N-C bond cleavage. A bimodal rotational state distribution of CO(v) has been observed, this result implies that isocyanic acid dissociates in the S₁ state in two different pathways.     

OPTICAL PROPERTIES OF δ-DOPED GaAs AND GaAs/Al0.1Ga0.9As SUPERLATTICES

Radiative transition in δ-doped GaAs superlattices with and without Al_0.1Ga_0.9As barriers is investigated by using photoluminescence at low temperatures. The experimental results show that the transition mechanism of δ-doped superlattices is very different from that of ordinary superlattices. Emission intensity of the transition from the electron first excited state to hole states is obviously stronger than that from the electron ground state to hole states due to larger overlap integral between wavefunctions of electrons in the first excited state and hole states. Based on the effective mass theory we have calculated the self-consistent potentials, optical transition matrix elements and photoluminescence spectra for two different samples. By using this model we can explain the main optical characteristics measured. Moreover, after taking into account the bandgap renormalization energy, good agreement between experiment and theory is obtained.     

Quasi-classical trajectory study of the stereodynamics of a Ne+H2+→NeH++H reaction

We have carried out a quasi-classical trajectory calculation for the reaction of Ne + H₂⁺ (v=0, j=1) → NeH⁺ + H on the ground state (1²A') using the LZHH potential energy surface constructed by Lü et al. [Lü S J, Zhang P Y, Han K L and He G Z 2010 J. Chem. Phys. 132 014303]. Differential cross sections at many collision energies indicate that the reaction is dominated by forward-scattering. In addition, the NeH⁺ product shows rotationally hot and vibrationally cold distributions. Stereodynamical results indicate that the products are strongly polarized in the direction perpendicular to the scattering plane and that the products rotate mainly in planes parallel to the scattering plane.     

State-to-state dynamics of F(~2P) + HO(~2Π) → O(~3P) + HF(~1Σ~+)reaction on 1~3A〞 potential energy surface

State-to-state time-dependent quantum dynamics calculations are carried out to study F(~2P) + HO(~2Π) → O(~3P) +HF(~1Σ~+) reaction on 1~3A〞 ground potential energy surface(PES). The vibrationally resolved reaction probabilities and the total integral cross section agree well with the previous results. Due to the heavy–light–heavy(HLH) system and the large exoergicity, the obvious vibrational inversion is found in a state-resolved integral cross section. The total differential cross section is found to be forward–backward scattering biased with strong oscillations at energy lower than a threshold of 0.10 eV, which is the indication of the indirect complex-forming mechanism. When the collision energy increases to greater than 0.10 eV, the angular distribution of the product becomes a strong forward scattering, and almost all the products are distributed at θ_t = 0°. This forward-peaked distribution can be attributed to the larger J partial waves and the property of the F atom itself, which make this reaction a direct abstraction process. The state-resolved differential cross sections are basically forward-backward symmetric for v' = 0, 1, and 2 at a collision energy of 0.07 eV; for a collision energy of 0.30 eV,it changes from backward/sideward scattering to forward peaked as v increasing from 0 to 3. These results indicate that the contribution of differential cross sections with more highly vibrational excited states to the total differential cross sections is principal, which further verifies the vibrational inversion in the products.     

Muon transfer in dµ + H2 collisions

The impact of excited state muon transfer in dμ + H₂ collisions has been investigated. The formation of metastable pdμ^* molecules and their subsequent decay into the pμ (1s) + d channel opens a transfer channel that is otherwise closed at the n=2 level. This mechanism enlarges the fraction of muons arriving to the ground state of the lighter isotope. The resulting ground state population P _1s ^pμ as function of deuterium concentration appears to be in qualitative agreement with recent measurements of the K _α X-ray yield in H₂/D₂ mixtures. This revised version was published online in August 2006 with corrections to the Cover Date.     

Isospin effect of the in-medium nucleon-nucleon cross section in excited nuclear reactions

Using relativistic mean field theory, the neutron and the proton density distribution of ⁵⁶Ni nuclei could be obtained in the ground state and the excited state. Based on the framework of the quantum molecular dynamics model, the ⁵⁶Ni nuclei have been simulated in ground state and in the neutron or proton excited state. We then used the three different states of ⁵⁶Ni to collide with the ⁵⁶Ni in the ground state. To discuss the evolution of the nuclear stopping in different reactions, two kinds of different excited nuclear reactions were studied at different reaction energies and at different impact parameters. Studies have shown that the nuclear stopping of an excited nuclear reaction is sensitive to the isospin-dependent in-medium nucleon-nucleon cross section, compared with the response value of the ground state nuclear reaction. So, it is better for the excited nuclei to extract the isospin dependence of nucleon-nucleon cross section information.     

CALCULATIONS OF STRETCHING VIBRATIONAL ENERGY LEVELS OF THE CH3I MOLECULE BY A NONLINEAR MODEL

A nonlinear model, i.e. the quantized discrete self-trapping equation, is applied to calculate the highly excited CH stretching vibrational energy levels of the CH₃I molecule in the liquid phase at the electronic ground state up to n=8. The obtained results agree well with the experimental data and with those obtained from local mode model calculations. We note that the dominant feature of the methyl CH stretching vibrational energy levels of the CH₃I molecule is a pattern of local mode pairs. When n≥7, all the vibrational energy of the CH₃ group can nearly be localized on a single CH bond.     

Non-adiabatic quantum dynamical studies of Na(3p) + HD(v = 1, j5) = 0)→NaH/NaD + D/H reaction

Non-adiabatic dynamical calculations are carried out for the Na(3 p)+HD(ν = 1, j = 0)→NaH/NaD+D/H reaction on the diabatic potential energy surfaces of Wang et al.(Sci. Rep. 2018, 8, 17960) by using the time-dependent wave packet method. The state-to-state integral cross sections and differential cross sections of two reaction channels(NaH/NaD+D/H)are calculated for collision energy up to 0.4 eV. The cross section branching ratio indicates that the dominant reaction channel changes from NaD+H to NaH+D when the collision energy is larger than 0.227 eV. The products from two reaction channels both prefer to form in vibrationally cold but rotationally hot states, and they both tend to forward scattering.     

INVESTIGATIONS ABOUT THE DYNAMICAL ELECTRON SCATTERING BY A HEXAGON-PRISM β-Si3N4 WHISKER

The dynamical electron scattering effects by a hexagon-prism β-Si₃N₄ whisker were investigated. The 002 dark field images of the wedges of the whisker along [110] direction showed sinusoidal fringes, in which there existed great differences in fringe period under two- and N-beam conditions. Fine structures of the corresponding diffraction spots under two-beam condition were also very different from those under many-beam condition. Such dynamical scattering effects were analyzed quantitatively.     

H+CH3D→H2+CH2D反应的十维量子动力学研究

本文采用最近发展的十维含时波包方法研究了H+CH₃D→H₂+CH₂D反应的模式选择性,计算了反应物CH₃D在基态、CH₃对称和不对称伸缩振动激发态、CD伸缩振动激发态以及CH₃弯曲模式的基频和倍频激发态等6个初始状态下的反应几率. 计算结果表明,在碰撞能0.0∽1.0 eV区间内,激发CH₃的任意一种伸缩振动模都能增强反应活性,而CD伸缩振动激发对反应的促进作用不明显. CH₃弯曲振动模的基频激发对促进反应活性几乎没有影响,由于CH₃对称伸缩振动模的基频与CH₃弯曲振动模倍频之间的费米共振作用,CH₃弯曲振动模的倍频激发显著增强了反应活性.     

Thermal expansion of solid CH4 and CD4

The linear expansion coefficients of solid light methane CH₄ and deuteromethane CD₄ have been denned in the temperature range 10°–24°K and 6°–58°K, respectively. The question about the nature of rotational motion of molecules in CH₄ and CD₄ crystals and about the existence of low temperature phase transition in solid methane is discussed.     

Absolute Raman intensities of CH4, CH3D,CH2D2, CHD3, and CD4

Measurements of the absolute vibrational Raman intensities and depolarization ratios for the fundamental and some overtone and combination bands of CH₄, CH₃D, CH₂D₂, CHD₃, and CD₄ are reported. Experimental aspects of these measurements are discussed. The experimental data conform satisfactorily to all isotope intensity sum rules. The measured intensities and depolarization ratios, together with the vibrational potential function for CH₄, make possible the calculation of the four independent parameters of the isotopic invariant quantities $\text{α}{}^{\mathrm{S}}\text{= |}\text{?α}\text{?S}\text{|}$. The results deduced from these agree with all 36 experimentally observed values. Values of electro-optical parameters for the CH bond are calculated and discussed.     

Low temperature far IR spectra of (CH34)N NiCl3, (CH3)4N NiBr3 and (CD3)4N NiBr3

The known phase transition in (CH₃)₄N NiCl₃, at 171 K, has been characterised by far IR spectroscopy. The transition is explained as due to a formation of weak labile C-H,…, Cl hydrogen bonds at low temperatures, restricting the “free” internal rotations of the methyl groups and perhaps at the same time ordering the orientations of the tetramethylammonium ions. No similar transition in (CH₃)₄N NiBr₃ was found.     

Relation between electrooptical constants and polar tensors of CH3F,CD3F,CH3Cl,CD3Cl,CH3Br,CD3Br,CD3I,and CD3I

Infrared intensity analysis was done in two ways. In one approach, formulas connecting electrooptical parameters (eop's) and intensities were derived and, using the intensities, the former were obtained. In evaluating the eop's the intensity sum equations were used directly so that the sign ambiguity of $\text{δP}\text{δQ}$ is avoided. In the other method, polar tensors were obtained directly from intensities. The two methods have now been connected, and polar tensors have been obtained in terms of electrooptical parameters so that the former were also free from sign ambiguity of $\text{δP}\text{δQ}$. They compare well with those obtained directly from intensities. In similar connecting formulas by other authors [see, for example, P. L. Prasad, J. Chem. Phys., 69, 4403, (1978)], both polar tensors and eop's were affected by the sign ambiguity.     

Time-dependent quantum dynamics study for reaction of D+CH4→CH3+HD

The semirigid vibrating rotor target (SVRT) model has been applied to the study of the reaction of D+CH_4→CH_3+HD using a time-dependent wave packet method. The energy dependence of the calculated reaction probability shows oscillatory structures similar to those observed in the abstraction reaction of H+H_2, H+CH_4 etc. We have also studied the influence of rotational and vibrational excitation of the reacting molecule (CH_4) on reaction probability. The excitation of the H－CH_3 stretching vibration gives significant enhancement of reaction probability, which rises significantly with the enhancement of rotational quantum number j. Finally, we have compared the cross section and the rate constant of the D+CH_4 system with that of the H+CH_4 system.     

Analysis of torsional splittings in the microwave spectra of dimethylether,CH3OCH3 and its isotopes,CD3OCH3 and CD3OCD3

The multiplet splitting patterns of microwave transitions in the ground state and the first two torsional excited states of CH₃OCH₃, CD₃OCD₃, and CD₃OCH₃ were analyzed in terms of the semirigid rotor models C_2vF-C_3vT-C_3vT and $\text{C}{}_3\text{F-}\text{C}{}_{\mathrm{3v}}\text{T-}\text{C}{}_{\mathrm{3v}}\text{T}\text{?}$. The following nonzero potential coefficients were obtained for CH₃OCH₃: V₃₀ = V₀₃ = 909.05 ± 0.49 cm^?1, V′₃₃ = 5.06 ± 1.60 cm^?1; for CD₃OCH₃: V₃₀(CD₃) = 897.18 ± 2.41 cm^?1, V₀₃(CH₃) = 910.45 ± 0.33 cm^?1; for CD₃OCD₃: V₃₀ = V₀₃ = 897.00 cm^?1. These results are compared to earlier microwave studies of these molecules.     

Vibrational relaxation in CD4 and CD4-rare gas mixtures

Using the optic-acoustic effect, measurements of the relaxation time were made after exciting the v₄ mode of CD₄. This was done for pure CD₄ and for mixtures of CD₄ with He, Ne, Ar and Kr, the results being 3.9±0.2, 1.8±0.2, 18±2, 70±15 and ? 100 μs at 1 atm, respectively. From the relaxation time dependence on mass as well as from a comparison between results for CH₄ and CD₄ it is concluded that energy transfer takes place via a vibration-rotation-translation (V-R-T) mechanism.Experiments were also conducted to study the most probable deexcitation path from the higher energy mode, v₃, to translation. This was done for CD₄-CD₄ as well as for CD₄-atom collisions. For pure CD₄ deexcitation occurs via the lower energy group (v₂, v₄), while for CD₄ mixtures it may also occur via the higher energy group (v₁, 2v₂, v₂ + v₄, 2v₄).     

Pionic x-ray intensities from C,CH2 and CD2

The relative intensities of the carbon L_α and L_β pionic X-ray lines from graphite, polythylene, and deuterated polyethylene have been measured. No differences between CH₂ and CD₂ were observed, but differences were found between graphite and the two polyethylene targets.     

K-shell excitation of CH4, NH3, H2O,CH3OH,CH3OCH3 and CH3NH2 by 2.5 keV electron impact

The regions around the respective carbon, nitrogen and oxygen K-edges of CH₄, NH₃, H₂O, CH₃OH, CH₃OCH₃ and CH₃NH₂ have been investigated by electron energy loss spectroscopy using a beam of 2.5 keV electrons. All spectra show a number of discrete peaks just below the K-shell ionization threshold. These discrete structures have been interpreted as being associated with the promotion of a K-shell electron to Rydberg orbitals which converge to the K-shell ionization threshold.     

Stereodynamics in reaction O（1D） ＋ CH4 〉OH ＋ CH3

A theoretical study of the stereodynamics for reaction O(1D) + CH4→OH + CH3 has been carried out using the quasiclassical trajectory method(QCT) on a potential energy surface structured by Gonzalez et al. The integral cross sections(ICSs), differential cross sections(DCSs) and product rotational angular momentum polarization have been calculated. With the collision energy increasing, the ICS decreases. There is no threshold energy, because no barrier is found on the minimum energy path. The DCS results show that the backward and forward scatterings exist at the same time. With the collision energy increasing, the dominant rotation of the product changes from the right-handed direction to the left-handed direction in planes parallel to the scattering plane. In the isotopic effect study, the decrease of the mass factor weakens the polarization degree of the rotational angular momentum vectors of the products.