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1.
Collision-induced photon emissions (CIE) were observed for keV CO2/He collisions from 190 to 1020 nm. The emissions were assigned to the Δν=0 band of the CO2 B 2Σu+ → X 2Πg electronic transition and the Δν = +3, +2, +1, 0, −1, −2, −3 vibrational transition progression in the CO2 A 2Πu → X 2Πg electronic transition. The other peaks arise from the emissions of excited O· fragment atoms and the target gas. The relative intensities of the CO2 and O· emissions are independent of the ion translational energy above 3 keV, supporting the curve-crossing mechanism for collisional excitation. Investigation of the relative intensities within the A 2Πu → X 2Πg emission of CO2 indicates that the vibrational distribution is well described by the Franck-Condon principle at high collision energy, a consequence of short collision time but not necessarily an indication of vertical transitions. Below 3 keV ion translational energy, vibrational excitation in the A 2Πu electronic state was observed. The observation is consistent with the explanation that the reaction occurs at small impact parameters, in which short-range, repulsive interactions between the projectile and the target result in direct translational-vibrational excitation.  相似文献   

2.
For studying the adiabatic and nonadiabatic mechanisms of the ClO (X 2Π) + ClO (X 2Π) → ClOOCl → 2Cl (2 P u) + O2 (X 3Σ g ) reaction (1) and the ClO (X 2Π) + ClO (X 2Π) → ClOOCl → Cl2 (X 1Σ g +) + O2 (X 3Σ g ) reaction (2), we calculated, by partial geometry optimizations under the C2 constraint, the O–O and O–Cl dissociation potential energy curves (PECs) from the five low-lying states of ClOOCl at the CASPT2 level. The CASSCF minimum-energy crossing point (MECP) between the potential energy surfaces of the 1 1A ground state [correlating with the product of reaction (1)] and the 1 3B state [correlating with the product of reaction (2)] states was also determined. Based on the CAS calculation results (PECs, energies, and spin–orbit coupling at the MECP), we predict that reaction (1) occurs along pathway 1: ClO (X 2Π) + ClO (X 2Π) → ClOOCl (1 1A) → 2Cl (2 P u) + O2 (X 3Σ g ) and that reaction (2) occurs along pathway 2: ClO (X 2Π) + ClO (X 2Π) → ClOOCl (1 1A) → 1 1A/1 3B MECP (142.4 cm−1) → ClOOCl (1 3B) → Cl2 (X 1Σ g +) + O2 (X 3Σ g ). The needed energies (relative to the reactant) for pathways 1 and 2 are predicted to be 5.3 and 11.1 kcal/mol, respectively, which indicates that reaction (1) is more favorable than reaction (2). The present work supports the traditional photochemical model for ozone degradation: ClOOCl (1 1A), formed by two ClO (X 2Π), can directly produce O2 plus two Cl atoms.  相似文献   

3.
This study investigated the characteristics of an atmospheric pressure air-glow discharge with a liquid cathode. Distilled water was utilized as the cathode. The electric field strength, gas temperature as well as the emission intensity of some N2(C3Πu → B3Πg) and OH (A2Σ+ → X2Π) bands were measured at a discharge current ranging from 15 to 50 mA. Based upon the data obtained, the reduced electric field strength, E/N, and effective vibrational temperatures for N2(C3Πu, X1Σ g + ) and OH (A2Σ+) were examined. The electron energy distribution function (EEDF) and some electron parameters (average energy, electron density and rate coefficients) were obtained based on a numerical solution of the Boltzmann kinetic equation. The result showed that the EEDF was not in equilibrium and the effective vibrational temperatures for N2(C3Πu, X1Σ g + ) were essentially higher than the gas temperatures.  相似文献   

4.
For the most stable linear isomer of C3S in its X1Σ+ state a six-dimensional potential energy surface (PES) has been calculated ab initio by coupled cluster – connected triples (CCSD(T)) method. The analytic form of the PES has been transformed in a quartic force field in dimensionless normal coordinates and employed in calculations of spectroscopic constants using second-order perturbation theory. The PES and the full kinetic energy operator in internal coordinates have been used to calculate variationally the anharmonic ro-vibrational energies for J=0 and J=1. The two experimental band origins of C3S observed in the gas phase, ν1 and ν1+ν5ν5, agree very well with the theoretical values. The anharmonic ro-vibrational levels, including the bending modes up to 2200 cm−1, are reported. The singlet ground state PES has a saddle point at about 1.25 eV above the linear minimum and two other higher lying cyclic local minima. The only dipole- and spin-allowed electronic transition between 0 and 5 eV is calculated to be the 1Π−X1Σ+ transition with a vertical transition energy of 353.2 nm in good agreement with the matrix value of 378 nm. The dissociative paths C + C2S, C2 + CS and C3 + S of low lying singlet and triplet states have been investigated. Electronic Supplementary Material: Supplementary material is available in the online version of this article at dx.doi.org/10.1007/s00214-005-0683-7 Dedicated to Professor H. Stoll.  相似文献   

5.
The kinetics of the 420 nm luminescence emitted from H2O and D2O polycrystalline Ih ices have been studied over the 77 to 162 K temperature range. In the case of both H2O and D2O ices, it was found that the luminescence rise and decay curves consisted of two luminescence components, and superimposing two first-order curves with different rate constants gave the best fit to the decay and rise curves. The mean lifetimes of the two luminescence components were 1.08 ± 0.03 s and 2.47 ± 0.03 s. The rate constants were found to have negligible temperature dependences, which led to activation energies well below those obtained for either activation-limited processes or even diffusion-limited processes. Furthermore, it was found that the luminescence kinetics were not affected by isotopic substitution of D for H in the ice lattice. These observations suggest that the rate-determining step in the mechanism for the production of the luminescence is a slow (probably spinforbidden) electronic transition that can occur at two different rates due to the presence of two different types of trapping sites in the ice lattice. A possible candidate for the electronic transition is the 4Σ → X 2Π transition of excited OH. radicals and not the previously suggested and ubiquitous A 2Σ+X 2Π transition of this species. Published in Russian in Kinetika i Kataliz 2006, Vol. 47, No. 5, pp. 709–721. This text was submitted by the authors in English.  相似文献   

6.
Symmetry-adapted perturbation theory is extended to the (quasi) degenerate, open-shell case. The new formalism is tested in calculations of the interaction energies for a helium atom in the ground state interacting with an excited hydrogen atom. It is shown that the method gives satisfactory results if the coupling with higher Rydberg states of the dimer is small, as is the case for the A2Σ+,B2Π,E2Π,32Π, and 12Δ states of HeH. For the C2Σ+ state convergence of the method is very slow, but it can be improved by including the n=3 states in the model space. Received: 3 June 1998 / Accepted: 9 September 1998 / Published online: 7 December 1998  相似文献   

7.
The spin-orbit and the spin-spin coupling constants of the 4Πg state of the He2 ion, of the parent a3Σu +, and of the b3Πg states of He2 have been evaluated by a multireference configuration interaction method. The theoretical spin-spin splittings of the a3Σu + state and the R-dependent spin-spin function are found to be in excellent agreement with experiment, with deviations in the range of a few MHz. The theoretical spin-orbit constants and splittings of the b3Πg state are larger than the experimental values by about 370 MHz. The spin-orbit coupling constant of the 4Πg state of He2 is␣estimated to be three times smaller than in the b3Πg state, but one of the intramultiplet off-diagonal spin-spin interactions is predicted to give a large contribution to the fine structure of the metastable ion. The theoretical fine structure constants for the He2 ion are expected to␣aid future spectroscopic investigations of the fine structure splittings of the negative ion. Received: 14 April 1998 / Accepted: 27 July 1998 / Published online: 19 October 1998  相似文献   

8.
Polymorphism of paracetamol   总被引:1,自引:0,他引:1  
The thermodynamic relationship between crystal modifications of paracetamol was studied by alternative methods. Temperature dependence of saturated vapor pressure for polymorphic modifications of the drug paracetamol (acetaminophen) was mea sured and thermodynamic functions of the sublimation process calculated. Solution calorimetry was carried out for the two modifications in the same solvent. Thermodynamic parameters for sublimation for form I (monoclinic) were found: ΔG sub298=60.0 kJ mol−1; ΔH sub298=117.9±0.7 kJ mol−1; ΔS sub298=190±2 J mol−1 K−1. For the orthorhombic modification (form II), the saturated vapor pressure could only be studied at 391 K. Phase transition enthalpy at 298 K, ΔH tr298(I→II)=2.0±0.4 kJ mol−1, was derived as the difference between the solution enthalpies of the noted polymorphs in the same solution (methanol). Based on ΔH tr298 (I→II), differences between temperature dependencies of heat capacities of both modifications and the vapor pressure value of form II at 391 K, the temperature dependence of saturated vapor pressure and thermodynamic sublimation parameters for modification II were also estimated (ΔG sub298=56.1 kJ mol−1; ΔH sub298=115.9±0.9 kJ mol−1; ΔS sub298=200±3 J mol−1 K−1). The results indicate that the modifications are monotropically related, which is in contrast to findings recently reported found by classical thermochemical methods.  相似文献   

9.
The vibrational, rotational, and centrifugal constants are calculated for the B 1Π u , C 1Π u , (1) 1Π g , and (2) electronic states of a 85Rb2 molecule. The calculations are based on the semi-empirical potential curves obtained in this work. The results from calculating the molecular constants are compared with experimental data. The Franck-Condon factors and R v′v″ centroids are calculated for the electronic transitions B 1Π u -X 1Σ g +, C 1Π u -X 1Σ g +, C 1Π u -(1) 1Π g , and C 1Π u -(2) 1Σ g +.  相似文献   

10.
The molar heat capacities of the room temperature ionic liquid 1-butylpyridinium tetrafluoroborate (BPBF4) were measured by an adiabatic calorimeter in temperature range from 80 to 390 K. The dependence of the molar heat capacity on temperature is given as a function of the reduced temperature X by polynomial equations, C p,m [J K−1 mol−1]=181.43+51.297X −4.7816X 2−1.9734X 3+8.1048X 4+11.108X 5 [X=(T−135)/55] for the solid phase (80–190 K), C p,m [J K−1 mol−1]= 349.96+25.106X+9.1320X 2+19.368X 3+2.23X 4−8.8201X 5 [X=(T−225)/27] for the glass state (198–252 K), and C p,m[J K−1 mol−1]= 402.40+21.982X−3.0304X 2+3.6514X 3+3.4585X 4 [X=(T−338)/52] for the liquid phase (286–390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BPBF4 relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass transition of BPBF4 was observed at 194.09 K, the enthalpy and entropy of the glass transition were determined to be ΔH g=2.157 kJ mol−1 and ΔS g=11.12 J K−1 mol−1, respectively. The result showed that the melting point of the BPBF4 is 279.79 K, the enthalpy and entropy of phase transition were calculated to be ΔH m = 8.453 kJ mol−1 and ΔS m=30.21 J K−1 mol−1. Using oxygen-bomb combustion calorimeter, the molar enthalpy of combustion of BPBF4 was determined to be Δc H m0 = −5451±3 kJ mol−1. The standard molar enthalpy of formation of BPBF4 was evaluated to be Δf H m0 = −1356.3±0.8 kJ mol−1 at T=298.150±0.001 K.  相似文献   

11.
The yields of post-source decay (PSD) and time-resolved photodissociation (PD) at 193 and 266 nm were measured for singly protonated leucine enkephalin ([YGGFL + H]+), a benchmark in the study of peptide ion dissociation, by using tandem time-of-flight mass spectrometry. The peptide ion was generated by matrix-assisted laser desorption ionization (MALDI) using 2,5-dihydroxybenzoic acid as the matrix. The critical energy (E0) and entropy (ΔS‡ at 1000 K) for the dissociation were determined by Rice-Ramsperger-Kassel-Marcus fit of the experimental data. MALDI was done for a mixture of YGGFL and Y6 and the plume temperature determined by the kinetic analysis of [Y6 + H]+ data were used to improve the precision of E0 and ΔS‡ for [YGGFL + H]+. E0 and ΔS‡ thus determined (E0 = 0.67 ± 0.08 eV, ΔS‡=−24.4 ± 3.2 eu with 1 eu = 4.184 J K−1mol−1) were significantly different from those determined by blackbody infrared radiative dissociation (BIRD) (E0 = 1.10 eV, ΔS‡ = −14.9 eu), and by surface-induced dissociation (SID) (E0 = 1.13 eV, ΔS‡ = −10.3 eu). Analysis of the present experimental data with the SID kinetics (and BIRD kinetics also) led to an unrealistic situation where not only PSD and PD but also MALDI-TOF signals could not be detected. As an explanation for the discrepancy, it was suggested that transition-state switching occurs from an energy bottleneck (SID/BIRD) to an entropy bottleneck (PSD/PD) as the internal energy increases.  相似文献   

12.
 The electronic structure of the TiSi molecule was examined using two types of multireference single and double excitation configuration interactions with highly extended basis sets, one including valence correlation and the other including valence and core–valence correlation. A multireference coupled-pair approximation (MRCPA) was further applied to the latter. The calculations suggest a 5Δ ground state, and the lowest excited state is 3Π and is only slightly (0.12 eV as estimated by MRCPA) above the ground state. The spectroscopic constants of the low-lying 1Δ, 3Δ, 1Π, 5Π, and 7Σ+ states as well as the 5Δ ground state and the 3Π excited states were evaluated, and we found that the molecule has only a weak σ bond and that six of the eight valence electrons essentially do not contribute to the bonding. The bonding nature of TiSi in these states is discussed in comparison with the TiC molecule. Received: 7 October 2000 / Accepted: 8 January 2001 / Published online: 3 May 2001  相似文献   

13.
The N-loss predissociation mechanisms of the A 2Σ+ (2 2 A′) state of N2O+ to the first and second dissociation limits were studied in the C s symmetry. The potential energy curves (PECs) and minimum energy crossing points (MECPs) for the C s states of N2O+ were calculated at the CAS levels. On the basis of our CAS calculation results (CASPT2 energetic results and CASSCF spin orbit couplings), we suggest two processes for N-loss predissociation mechanisms of A 2Σ+ (2 2 A′) to the first and second limits. The first two steps in the two processes are the same: A 2Σ+ passes through the 2 2 A′/1 4 A″ MECP and then reaches the 1 4 A″ (1 4Σ) PEC. The 2 2 A′/1 4 A″ MECP has a bent geometry and is slightly higher in energy than the transition state along the 1 4 A″ PEC. Our mechanisms are different from the previously suggested mechanisms (via 1 4Π).  相似文献   

14.
15.
Four nickel carbonate-bearing minerals from Australia have been investigated to study the effect of Ni for Mg substitution. The spectra of nullaginite, zaratite, widgiemoolthalite and takovite show three main features in the range of 26,720–25,855 cm−11-band), 15,230–14,740 cm−12-band) and 9,200–9,145 cm−13-band) which are characteristic of divalent nickel in six-fold coordination. The Crystal Field Stabilization Energy (CFSE) of Ni2+ in the four carbonates is calculated from the observed 3A2g(3F) → 3T2g(3F) transition. CFSE is dependent on mineralogy, crystallinity and chemical composition (Al/Mg-content). The splitting of the ν1- and ν3-bands and non-Gaussian shape of ν3-band in the minerals are the effects of Ni-site distortion from regular octahedral. The effect of structural cation substitutions (Mg2+, Ni2+, Fe2+ and trivalent cations, Al3+, Fe3+) in the carbonate minerals is noticed on band shifts. Thus, electronic bands in the UV–Vis–NIR spectra and the overtones and combination bands of OH and carbonate ion in NIR show shifts to higher wavenumbers, particularly for widgiemoolthalite and takovite.  相似文献   

16.
A quasi-classical trajectory (QCT) calculation with the fourth-order explicit symplectic algorithm for the N(4S) + O2(X3Σg) → NO(X2Π) + O(3P) reaction has been performed by employing the ground and first-excited potential energy surfaces (PESs). Since the translational temperature considered is up to 5000 K, the larger relative translational energy and the higher vibrational and rotational level of O2 molecule have been taken into account. The affect of the relative translational energy, the vibrational and rotational level of O2 molecule in the reaction cross-sections of the ground and first-excited PESs has been discussed in a extensive range. And we exhibit the dependence of microscopic rate constants on the vibrational and rotational level of O2 molecule at T = 4000 K. The thermal rate constants at the translational temperature betweem 300 and 5000 K have been evaluated and the corresponding Arrhenius curve has been fitted for reaction (1). It is found by comparison that the thermal rate constants determined in this work have a better agreement with the experimental data and provide a more valid theoretical reference.  相似文献   

17.
Isothermal titration calorimetry was applied for studying the binding interactions of cyclic and linear surfactins with different ionic charge (z= −2 and −3) and lipid chain length (n=14 and 18) to 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidyl-choline (POPC) vesicles in 10mMTris buffer at pH8.5with 150mMNaCl at 25°C. Surfactin analogues interacted spontaneously (ΔG D w→b < 0) with POPC vesicles. The binding reactions were endothermic (ΔH D w→b > 0) and entropy-driven process (ΔS D w→b > 0). Moreover, significant differences in the binding constant values (K) ranging from 6.6·103 to 9.6·104 M−1 show that cyclic structure and the increase of lipid chain length are favourable on the surfactin binding affinity to POPC vesicles, whereas the rise of the number of negative charges has an opposite effect.  相似文献   

18.
The molar heat capacities of the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluoroborate (BMIPF6) were measured by an adiabatic calorimeter in temperature range from 80 to 390 K. The dependence of the molar heat capacity on temperature is given as a function of the reduced temperature (X) by polynomial equations, C P,m (J K−1 mol−1) = 204.75 + 81.421X − 23.828 X 2 + 12.044X 3 + 2.5442X 4 [X = (T − 132.5)/52.5] for the solid phase (80–185 K), C P,m (J K−1 mol−1) = 368.99 + 2.4199X + 1.0027X 2 + 0.43395X 3 [X = (T − 230)/35] for the glass state (195 − 265 K), and C P,m (J K−1 mol−1) = 415.01 + 21.992X − 0.24656X 2 + 0.57770X 3 [X = (T − 337.5)/52.5] for the liquid phase (285–390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BMIPF6 relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass transition of BMIPF6 was measured to be 190.41 K, the enthalpy and entropy of the glass transition were determined to be ΔH g = 2.853 kJ mol−1 and ΔS g = 14.98 J K−1 mol−1, respectively. The results showed that the milting point of the BMIPF6 is 281.83 K, the enthalpy and entropy of phase transition were calculated to be ΔH m = 20.67 kJ mol−1 and ΔS m = 73.34 J K−1 mol−1.  相似文献   

19.
The Gibbs free energies of solvation (ΔG s) and the electronic structures of endohedral metallofullerenes M+@C60 (M+= Li+, K+) were calculated within the framework of the density functional theory and the polarizable continuum model. In water environment, the equilibrium position of K+ is at the center of the fullerene cavity whereas that of Li+ is shifted by 0.14 nm toward the fullerene cage. The Li+ cation is stabilized by interactions with both the fullerene and solvent. The equilibrium structures of both endohedral metallofullerenes are characterized by very close ΔG s values. In particular, the calculated ΔG s values for K+@C60 are in the range from −124 to −149 kJ mol−1 depending on the basis set and on the type of the density functional. Molecular dynamics simulations (TIP3P H2O, OPLS force field, water sphere of radius 1.9 nm) showed that the radial distribution functions of water density around C60 and M+@C60 are very similar, whereas orientations of water dipoles around the endohedral metallofullerenes resemble the hydration pattern of isolated metal ions.  相似文献   

20.
Two states of CO which are expected to live longer than the well-known 2Π shape resonance are examined and the results obtained are compared with the analogous states of the isoelectronic N2 system. The 4Σ and 4Π states are found to be stable with respect to dissociation. The latter state is also stable with respect to single-electron loss to its parent neutral state. The lifetime of this state is supposed to be long, but not necessarily long enough to allow detection in a mass spectrometer. Received: 28 May 1998 / Accepted: 23 July 1998 / Published online: 9 October 1998  相似文献   

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