Atmospheric reactions Cl+CH3-(CH2)n-OH (n=0-4): a kinetic and theoretical study

The reactions of Cl with a series of linear alcohols: methanol (k1), ethanol (k2), 1-propanol (k3), 1-butanol (k4), and 1-pentanol (k5) were investigated as a function of temperature in the range of 264-382 K by laser photolysis-resonance fluorescence. The obtained kinetic data were used to derive the following Arrhenius expressions: k1=(3.55+/-0.22)x10(-10) exp[-(559+/-40)T], k2=(5.25+/-0.52)x10(-11) exp[(190+/-68)T], k3=(2.63+/-0.21)x10(-11) exp[(525+/-51)T], k4=(3.12+/-0.31)x10(-11) exp[(548+/-65)T], and k5=(3.97+/-0.48)x10(-11) exp[(533+/-77)T] (in units of cm(3) molecule(-1) s(-1)). To our knowledge, these are the first absolute kinetic data reported for 1-butanol and 1-pentanol and also the first kinetic study as a function of temperature for these two compounds. Results, mechanism, and tropospheric implications are discussed and compared with the reported reactivity with OH radicals. Moreover, a theoretical insight into the mechanisms of these reactions has also been pursued through ab initio M?ller-Plesset second-order perturbation treatment calculations with 6-311G** basis sets. Optimized geometries and vibrational frequencies have been obtained for transition states and molecular complexes appearing along the different reaction pathways. Furthermore, molecular energies have been calculated at quadratic configuration interaction with single, double, and triple excitations level in order to get an estimation of the activation energies.     

ΔF = ±2 transitions in the hyperfine spectrum of Er I

The occurrence of 15ΔF=±2 transitions in the hyperfine spectrum of five lines of Er I was observed by means of high-resolution laser-atomic-beam spectroscopy. These normally forbidden transitions are caused by an external magnetic field which mixes closely lying hyperfine levels that have neighbouringF quantum numbers. If the Zeeman splittings under the applied magnetic field are small compared to the hyperfine splittings, the intensities of theΔF=±2 components are proportional to the square of the magnetic field strength. Under the variation of the laser intensity theΔF=±2 transitions show the same behaviour as homogeneously broadenedΔF=0, ±1 transitions. The relative intensities between theΔF=±2 components as well as the intensity ratios of theΔF=±2 to neighbouringΔF=±1 components are studied and interpreted in terms of first order perturbation theory.     

The hyperfine structure of the predissociated stateB′0+ of IBr

TheB′0⁺ state of IBr is strongly predissociated which leads to fragmentary rovibrational structure and level broadening. Using Doppler free laser polarization spectroscopy, the hyperfine structure of the sharpest rotational lines of several band fragments in theB′?X system was investigated for the first time. The hyperfine analysis yields a strong vibrational dependence of the nuclear quadrupole interaction for Br and the nuclear spin-rotation interaction for I and Br. The magnitude of the hyperfine parameters and their variation with vibrational state are discussed in a configuration model for the bound and repulsive states according to the observed predissociation.     

The NaK 1(b) 3Pi(Omega=0) state hyperfine structure and the 1(b) 3Pi(Omega=0) approximately 2(A) 1Sigma+ spin-orbit interaction

We have measured the hyperfine structure of mutually perturbing rovibrational levels of the 1(b) 3Pi0 and 2(A) 1Sigma+ states of the NaK molecule, using the perturbation-facilitated optical-optical double resonance method with copropagating lasers. The unperturbed 1(b) 3Pi0 levels are split into four hyperfine components by the Fermi contact interaction bFIS. Mixing between the 1(b) 3Pi0 and 2(A) 1Sigma+ levels imparts hyperfine structure to the nominally singlet component of the perturbed levels and reduces the hyperfine splitting of the nominally triplet component. Theoretical analysis relates these observations to the hyperfine splitting that each 1(b) 3Pi0 level would have if it were not perturbed by a 2(A) 1Sigma+ level. Using this analysis, we demonstrate that significant hyperfine splitting arises because the 1(b) 3Pi0 state cannot be described as pure Hund's case (a). We determine bF for the 1(b) 3Pi0 levels and also a more accurate value for the magnitude of the singlet-triplet spin-orbit coupling HSO=[1(b) 3Pi0(vb,J)(H(SO))2(A) 1Sigma+(vA,J). Using the known spectroscopic constants of the 1(b) 3Pi state, we obtain bF=0.009 89+/-0.000 27 cm(-1). The values of (H(SO)) are found to be between 2 and 3 cm(-1), depending on vb, vA, and J. Dividing (H(SO)) by calculated vibrational overlap integrals, and taking account of the 1(b) 3Pi(Omega) rotational mixing, we can determine the magnitude of the electronic part H(el) of H(SO). Our results yield (H(el))=(16.33+/-0.15) cm(-1), consistent with our previous determinations using different techniques.     

Theoretical Study of CH3CH=CH2+O(1D) Reaction: Mechanism and Kinetics

The mechanism and kinetics for the reaction of propene(CH₃CH=CH₂) molecule with O(¹D) atom were investigated theoretically. The electronic structure information of the potential energy surface(PES) was obtained at the B3LYP/6-311+G(d,p) level, and the single-point energies were refined by the multi-level MCG3-MPWB method. The calculated results show that O(¹D) atom can attack CH₃CH=CH₂ via the barrierless insertion mechanism to form four energy-riched intermediates CH₃C(OH)CH₂(IM1), CH₃CHCHOH(IM2), CH₂OHCHCH₂(IM3) and cyclo- CH₂OCHCH₃(IM4), respectively, on the singlet PES. The branching ratios as well as the pressure- and temperaturedependence of various product channels for this multi-well reaction were predicted by variational transition-state and Rice-Ramsperger-Kassel-Marcus(RRKM) theories. The present results will be useful to gain a deep insight into the reaction mechanism and kinetics of CH₃CH=CH₂+O(¹D) reaction.     

The H + Li2 bimolecular exchange reaction: dynamical and kinetical properties at J = 0

For the first time in the literature, rigorous time-independent quantum scattering formalism was applied, by means of the ABC program, to the H + Li(2) → LiH + Li reaction. The state-to-state probabilities as a function of the total energy have been computed at zero total angular momentum (J = 0) allowing us to evaluate the effect of vibrational/rotational excitation on the reaction promotion/inhibition, the energetic distribution of products, and the temperature dependence of the J-shifting thermal rate coefficients.     

Polarization quantum beat spectroscopy of HCF(A1A"). I. 19F and 1H hyperfine structure and Zeeman effect

To further investigate the (19)F and (1)H nuclear hyperfine structure and Zeeman effect in the simplest singlet carbene, HCF, we recorded polarization quantum beat spectra (QBS) of the pure bending levels 2(0) (n) with n = 0-7 and combination bands 1(0) (1)2(0) (n) with n = 1-6 and 2(0) (n)3(0) (1) with n = 0-3 in the HCF A(1)A(")<--X(1)A(') system. The spectra were measured under jet-cooled conditions using a pulsed discharge source, both at zero field and under application of a weak magnetic field (<30 G). Analysis yielded the nuclear spin-rotation constants C(aa) and weak field Lande g(aa) factors. Consistent with a two-state model, the majority of observed vibrational levels exhibit a linear correlation of C(aa) and g(aa), and our analysis yielded effective (a) hyperfine constants for the (19)F and (1)H nuclei (in MHz) of 728(23) and 55(2), respectively. The latter was determined here owing to the high resolving power of QBS. The vibrational state selectivity of the (19)F hyperfine constants is discussed, and we suggest that the underlying Renner-Teller interaction may play an important role.     

Low-symmetry structures of Au32Z (Z = +1, 0, -1) clusters

In this work, we have explored new stable structures of the Au32Z (Z = +1, 0, -1) clusters. Theoretical calculations using density functional theory within the generalized-gradient approximation were performed. Our results show that, in the anion state (Au32-), low-symmetry (disordered) structures are preferred over the caged fullerene-like isomer. In addition, the cationic cluster (Au32+) also exhibits a disordered low-symmetry structure as its lowest energy configuration, but it is much closer in energy to the fullerene-like isomer. These results, obtained at T = 0 K, indicate that disordered structures for the Au32- and Au32+ clusters may be detected not only at room temperature, as was experimentally verified for the Au32- one, but also at much lower temperatures.     

Theoretical investigations on structure, electrostatics potentials and vibrational frequencies of Li+ - CH3- O- (CH2- CH2- O)n- CH3 (n=3-7) conformers

Electronic structure, charge distributions and vibrational characteristics of CH₃ O(CH₂ CH₂ O) _n CH₃ (n=3-7) have been derived using the ab initio Hartree Fock and density functional calculations. For tri- to hexaglymes the lowest energy conformers have trans- conformation around the C-C and C-O bonds of the backbone. For heptaglyme (n=7 in the series), however, gauche-conformation around the C-C bonds renders more stability to the conformer and turns out to be 10.1 kJ mol ⁻¹ lower in energy relative to the conformer having trans-orientation around the C-C and C-O bonds. The molecular electrostatic potential topographical investigations reveal deeper minima for the ether oxygen in conformers having the gauche conformation around the C-C bonds over those for the trans- conformers. A change from trans- to gauche-conformation around the C-C bonds of the lowest energy conformer of heptaglyme engenders a triplet of intense bands ∼1,150 cm ⁻¹ in the vibrational spectra. Theoretical calculations predict that Li ⁺ binds strongly to the heptaglyme conformer in the above series. The frequency shifts in the vibrational spectra of CH₃O(CH₂CH₂O) _n CH₃- Li⁺ (n=3-7) conformers have been discussed     

ΔF = 2–6 transitions in the hyperfine spectrum of λ = 601.8 nm line of 151Eu

The magnetic field effect of the a ⁸ S _1/2-z ⁸ P _9/2, F = 7 transition lines of ¹⁵¹Eu in magnetic fields up to 400 Gauss has been studied by using laser-atomic-beam-spectroscopy. δF = 2–6 transitions were observed. Results show that the transitions originate from the mixing of the Zeeman states induced by the magnetic field. The condition favourable to observation of the |δF| ≥ 2 transitions especially the transitions with high |δF| values discussed     

Unimolecular reactions of the isolated immonium ions CH3CH = NH+C4H9, CH3CH2Ch = NH+C4H9 and (CH3)2C = NH+C4H9

The reactions of ten metastable immonium ions of general structure R¹R²C?NH⁺C₄H₉ (R¹ = H, R² = CH₃, C₂H₅; R¹ = R² = CH₃) are reported and discussed. Elimination of C₄H₈ is usually the dominant fragmentation pathway. This process gives rise to a Gaussian metastable peak; it is interpreted in terms of a mechanism involving ion-neutral complexes containing incipient butyl) cations. Metastable immonium ions ontaining an isobutyl group are unique in undergoing a minor amount of imine (R¹R²C?NH) loss. This decomposition route, which also produces a Gaussian metastable peak, decreases in importance as the basicity of the imine increases. The correlation between imine loss and the presence of an isobutyl group is rationalized by the rearrangement of the appropriate ion-neutral complexes in which there are isobutyl cations to the isomeric complexes containing the thermodynamically more stable tert-butyl cations. A sizeable amount of a third reaction, expulsion of C₃H₆, is observed for metastable n-C₄H₉ ⁺NH?CR¹R² ions; in contrast to C₄H₈ and R¹R²C?NH loss, C₃H₆ elimination occurs with a large kinetic energy release (40–48 kJ mol^?1) and is evidenced by a dish-topped metastable peak. This process is explained using a two-step mechanism involving a 1,5-hydride shift, followed by cleavage of the resultant secondary open-chain cations, CH₃CH⁺ CH₂CH₂NHCHR¹R².     

Imaging the pair-correlated excitation function: The F+CH4-->HF(v')+CH3(nu=0) reaction

The velocity map ion imaging technique was applied to measure the reaction excitation function for the first time. It was found that the "raw" excitation function was significantly distorted by the density-to-flux transformation of the title reaction. Through a systematic investigation, possible reasons for such a dramatic effect are outlined. In addition, the state-resolved, pair-correlated excitation functions and branching ratios are presented. Effects of imperfect time slicing in the time-sliced velocity imaging technique in general are also discussed.     

Strong intramolecular Si-N interactions in the chlorosilanes Cl3-nHnSiOCH2CH2NMe2 (n = 1-3)

The compounds Cl 3SiOCH 2CH 2NMe 2 ( 1) and Cl 2HSiOCH 2CH 2NMe 2 ( 2) were prepared by reactions of lithium 2-(dimethylamino)ethanolate with SiCl 4 and HSiCl 3. The analogous reaction with H 2SiCl 2 gave ClH 2SiOCH 2CH 2NMe 2 ( 3), but only in a mixture with Cl 2HSiOCH 2CH 2NMe 2 ( 2), from which it could not be separated. All compounds were characterized by IR and NMR ( (1)H, (13)C, (29)Si) spectroscopy, 1 and 2 by elemental analyses and by determination of their crystal structures. Cl 3SiOCH 2CH 2NMe 2 ( 1) and Cl 2HSiOCH 2CH 2NMe 2 ( 2) crystallize as monomeric ring compounds with pentacoordinate silicon atoms participating in intramolecular Si-N bonds [2.060(2) A ( 1), 2.037(2) A ( 2)]. The dative bonds in 1 and 2 between the silicon and nitrogen atoms could also be proven to exist at low temperatures in solution in (1)H, (29)Si-HMBC-NMR experiments by detection of the scalar coupling between the (29)Si and the protons of the NCH 2 and NCH 3 groups. A function describing the chemical shift delta exp (29)Si dependent on the chemical shifts of the individual equilibrium components, the temperature, and the free enthalpy of reaction was worked out and fitted to the experimental VT-NMR data of 1 and 2. This provided values of the free reaction enthalpies of Delta G = -28.8 +/- 3.9 kJ x mol (-1) for 1 and Delta G = -22.3 +/- 0.4 kJ x mol (-1) for 2 and estimates for the chemical shifts of open-chain (index o) and ring conformers (index r) for 1 of delta r = -94 +/- 2 ppm and delta o = -36 +/- 5 ppm and for 2 of delta r = -82 +/- 1 ppm and delta o = -33 +/- 4 ppm. The value of delta r for 1 is very close to that obtained from a solid-state (29)Si MAS NMR spectrum. Quantumchemical calculations (up to MP2/TZVPP) gave largely differing geometries for 1 (with a Si...N distance of 3.072 A), but well reproduced the geometry of 2. These differences are due to Cl...H and Cl...C repulsions and solid state effects, which can be modeled by conductor-like screening model calculations and also rationalized in terms of the topology of the electron density, which was analyzed in terms of the quantum theory of atoms in molecules.     

CH4-nFn(n=1～3)与CH3氢抽提反应微观动力学的理论研究

采用量子化学的QCISD(T)/6-311 G(d,p)//BHandHLYP/6-311G(d,p)方法研究了氟代甲烷CH4-nFn(n=1~3)与CH3自由基氢抽提反应的微观动力学性质.并利用Polyrate程序分别计算了3个反应在200~3000K范围内的速率常数.计算结果表明,R1a,R2a和R3三个反应路径的反应能量分别为-12.7,-9.5和11.8kJ/mol,相应的能垒依次为67.0,62.2和67.5kJ/mol.在437K时,kCVT/SCT分别为6.72×10-19,8.01×10-18和8.82×10-20cm3/(molecule.s).计算结果还表明,在低温段反应的量子隧道效应显著,在计算温度范围内变分效应对反应速率常数的影响可以忽略.     

Doppler-free two-photon excitation spectroscopy and the Zeeman effects of the S1 1B1u(v21=1) <-- S0 1Ag(v=0) band of naphthalene-d8

Doppler-free two-photon excitation spectrum and the Zeeman effect of the S1 1B1u(v21=1) <-- S0 1Ag(v=0) transition of naphthalene-d8 have been measured. 908 lines of Q(Ka)Q(J)KaKc transition of J=0-41, Ka=0-20 were assigned, and the molecular constants of the S1 1B1u(v21=1) state were determined. Perturbations were observed, and those were identified as originating from Coriolis interaction. No perturbation originating from an interaction with triplet state was observed. The Zeeman splittings from lines of a given J were observed to increase with Kc, and those of the Kc=J levels increased linearly with J. The Zeeman effects are shown to be originating from the magnetic moment of the S1 1B1u state, which is along the c axis and is induced by mixing of the S2 1B3u state to the S1 1B1u state by J-L coupling. Rotationally resolved levels were found not to be mixed with a triplet state from the Zeeman spectra. Accordingly, it is concluded that nonradiative decay of an isolated naphthalene excited to low rovibronic levels in the S1 1B1u state does not occur through the intersystem mixing. This is at variance with generally accepted understanding of the pathways of the nonradiative decay.     

Electronic transitions in collinear H+ + D2 (ν = 0) → HD+ (ν = 0,1) + D via classical trajectories in complex time and complex phase space

A semiclassical treatment of electronic transitions in the collinear rearrangement H⁺ + D₂ (ν = 0) → HD⁺ (ν = 0,1) + D is presented. The treatment represents an extension of Stueckelberg's method for a single nuclear degree of freedom to collisions involving several nuclear degrees of freedom. The classical limit of scattering amplitudes (S-matrix elements) is calculated for the transition between the two adiabatic potential energy surfaces corresponding to the two lowest singlet states of HD⁺₂. S-matrix elements are constructed from trajectories propagating in complex time and complex phase space, which make localized transitions between the two surfaces by crossing their complex line of intersection. The action along each trajectory acquires an imaginary part, which contributes exponential damping to the corresponding amplitude for electronic transition.     

A time-dependent wave-packet quantum scattering study of the reaction H2+(v = 0-2,4,6;j = 1) + He--> HeH+ + H

The quantum scattering dynamics calculation was carried out for the titled reaction in the collision energy range of 0.0-2.4 eV with reactant H(2) (+) in the rotational state j = 1 and vibrational states v = 0-2, 4, and 6. The present time-dependent wave-packet calculation takes into account the Coriolis coupling (CC) and uses the accurate ab initio potential-energy surface of Palmieri et al. [Mol. Phys. 98, 1835 (2000)]. The importance of including the CC quantum scattering calculation has been revealed by the comparison between the CC calculation and the previous coupled state (CS) calculation. The CC total cross sections for the v = 2, 4, and 6 states show collision energy-dependent behaviors different from those based on the CS calculation. Furthermore, the collision energy dependence of the total cross sections obtained in the present CC calculation only exhibits minor oscillations, indicating that the chance is slim for reactive resonances in total cross sections to survive through the partial-wave averaging. The magnitude and profile of the CC total cross sections for v = 0-2 in the collision energy range of 0.0-2.5 eV are found to be consistent with experimental cross sections obtained recently by Tang et al. [J. Chem. Phys. 122, 164301 (2005)] after taking into account the experimental uncertainties.     

The J = 1 para levels of the v = 0 to 6 np singlet Rydberg series of molecular hydrogen revisited

The energies and the widths of the J = 1 para levels of the v = 0 to 6 Rydberg np singlet series of molecular hydrogen with absolute intensities of the R(0) and P(2) absorption lines were measured by a high - resolution synchrotron radiation experiment and calculated through a full ab initio multichannel quantum defect theory approach. On the basis of the agreement between theory and experiment, 31 levels were either reassigned or assigned for the first time.