Dissociative recombination of water cluster ions with free electrons: cross sections and branching ratios

Dissociative recombination (DR) of water cluster ions H(+)(H(2)O)(n) (n=4-6) with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). For the first time, branching ratios have been determined for the dominating product channels and absolute DR cross sections have been measured in the energy range from 0.001 to 0.7 eV. Dissociative recombination is concluded to result in extensive fragmentation for all three cluster ions, and a maximum number of heavy oxygen-containing fragments is produced with a probability close to unity. The branching ratio results agree with earlier DR studies of smaller water cluster ions where the channel nH(2)O+H has been observed to dominate and where energy transfer to internal degrees of freedom has been concluded to be highly efficient. The absolute DR cross sections for H(+)(H(2)O)(n) (n=4-6) decrease monotonically with increasing energy with an energy dependence close to E(-1) in the lower part of the energy range and a faster falloff at higher energies, in agreement with the behavior of other studied heavy ions. The cross section data have been used to calculate DR rate coefficients in the temperature range of 10-2000 K. The results from storage ring experiments with water cluster ions are concluded to partly confirm the earlier results from afterglow experiments. The DR rate coefficients for H(+)(H(2)O)(n) (n=1-6) are in general somewhat lower than reported from afterglow experiments. The rate coefficient tends to increase with increasing cluster size, but not in the monotonic way that has been reported from afterglow experiments. The needs for further experimental studies and for theoretical models that can be used to predict the DR rate of polyatomic ions are discussed.     

Dissociative recombination of fully deuterated protonated acetonitrile, CD3CND+: product branching fractions, absolute cross section and thermal rate coefficient

The dissociative recombination of fully deuterated protonated acetonitrile, CD(3)CND(+), has been investigated at the CRYRING heavy ion storage ring, located at the Manne Siegbahn Laboratory, Stockholm, Sweden. Branching fractions were measured at approximately 0 eV relative collision energy between the ions and the electrons and in 65% of the DR events there was no rupture of bonds between heavy atoms. In the remaining 35%, one of the bonds between the heavy atoms was broken. The DR cross-section was measured between approximately 0 eV and 1 eV relative collision energy. In the energy region between 1 meV and 0.1 eV the cross section data were best fitted by the expression sigma = 7.37 x 10(-16) (E/eV)(-1.23) cm(2), whereas sigma = 4.12 x 10(-16) (E/eV)(-1.46) cm(2) was the best fit for the energy region between 0.1 and 1.0 eV. From the cross section a thermal rate coefficient of alpha(T) = 8.13 x 10(-7) (T/300)(-0.69) cm(3) s(-1) was deduced.     

Dissociative recombination study of N(3) (+): cross section and branching fraction measurements

We report an investigation into the dissociative recombination of the azide radical cation, N(3) (+). The reaction rate constant has been measured to be 6.47 x 10(-7) cm(3) s(-1) at room temperature. This value is smaller than those reported earlier for the ion-electron neutralization of N(3) (+) at nitrogen atmospheric pressure. A strong propensity to dissociate through the N(2)+N channel has been observed.     

Dissociative recombination of H+(H2O)3 and D+(D2O)3 water cluster ions with electrons: cross sections and branching ratios

Dissociative recombination (DR) of the water cluster ions H(+)(H(2)O)(3) and D(+)(D(2)O)(3) with electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). For the first time, absolute DR cross sections have been measured for H(+)(H(2)O)(3) in the energy range of 0.001-0.8 eV, and relative cross sections have been measured for D(+)(D(2)O)(3) in the energy range of 0.001-1.0 eV. The DR cross sections for H(+)(H(2)O)(3) are larger than previously observed for H(+)(H(2)O)(n) (n=1,2), which is in agreement with the previously observed trend indicating that the DR rate coefficient increases with size of the water cluster ion. Branching ratios have been determined for the dominating product channels. Dissociative recombination of H(+)(H(2)O)(3) mainly results in the formation of 3H(2)O+H (probability of 0.95+/-0.05) and with a possible minor channel resulting in 2H(2)O+OH+H(2) (0.05+/-0.05). The dominating channels for DR of D(+)(D(2)O)(3) are 3D(2)O+D (0.88+/-0.03) and 2D(2)O+OD+D(2) (0.09+/-0.02). The branching ratios are comparable to earlier DR results for H(+)(H(2)O)(2) and D(+)(D(2)O)(2), which gave 2X(2)O+X (X=H,D) with a probability of over 0.9.     

Dissociative electron-ion recombination of the interstellar species protonated glycolaldehyde, acetic acid, and methyl formate

Recently, methyl formate, glycolaldehyde, and acetic acid have been detected in the Interstellar Medium, ISM. The rate constants, α(e), for dissociative electron-ion recombination of protonated gycolaldehyde, (HOCH(2)CHO)H(+), and protonated methyl formate, (HCOOCH(3))H(+), have been determined at 300 K in a variable temperature flowing afterglow using a Langmuir probe to obtain the electron density. The recombination rate constants at 300 K are 3.2 × 10(-7) cm(3) s(-1) for protonated methyl formate and 7.5 × 10(-7) cm(3) s(-1) for protonated glycolaldehyde. The recombination rate constant of protonated acetic acid could not be directly measured, but it appears to have a rate constant, α(e), on the 10(-7) cm(3) s(-1) scale. Several high- and low-temperature measurements for protonated methyl formate were made. In addition, an α(e) measurement at 220 K for protonated glycolaldehyde was performed. The astrochemical implications of the rates of recombination, α(e), and protonation routes are discussed.     

Dissociative recombination of the deuterated acetaldehyde ion, CD3CDO(+): product branching fractions, absolute cross sections and thermal rate coefficient

Dissociative recombination of the deuterated acetaldehyde ion CD3CDO(+) has been studied at the heavy-ion storage ring CRYRING, located at the Manne Siegbahn Laboratory, Stockholm, Sweden. Product branching fractions together with absolute DR cross-sections were measured. The branching fractions were determined at a relative collision energy between the ions and the electrons of approximately 0 eV. With a probability of 34% the DR events resulted in no ruptures of bonds between heavy atoms (i.e. no breakage of the C-C bond or the C[double bond, length as m-dash]O bond). In the remaining 66% of the events one of the bonds between the heavy atoms was broken. The energy-dependent cross-section for the DR reaction was measured between approximately 0 and 1 eV relative kinetic energy. In the energy region between 1 meV and 0.2 eV the absolute cross section could be fitted by the expression sigma(E) = 6.8 x 10(-16)E(-1.28) cm(2), whereas in the energy interval between 0.2 and 1 eV the data were best fitted by sigma(E) = 4.1 x 10(-16)E(-1.60) cm(2). From these cross section data the thermal rate coefficient (as a function of the electron temperature), alpha(T) = 9.2 x 10(-7) (T/300)(-0.72) cm(3) s(-1) was obtained.     

Dissociative recombination of the weakly bound NO-dimer cation: cross sections and three-body dynamics

Dissociative recombination (DR) of the dimer ion (NO)(2) (+) has been studied at the heavy-ion storage ring CRYRING at the Manne Siegbahn Laboratory, Stockholm. The experiments were aimed at determining details on the strongly enhanced thermal rate coefficient for the dimer, interpreting the dissociation dynamics of the dimer ion, and studying the degree of similarity to the behavior in the monomer. The DR rate reveals that the very large efficiency of the dimer rate with respect to the monomer is limited to electron energies below 0.2 eV. The fragmentation products reveal that the breakup into the three-body channel NO+O+N dominates with a probability of 0.69+/-0.02. The second most important channel yields NO+NO fragments with a probability of 0.23+/-0.03. Furthermore, the dominant three-body breakup yields electronic and vibrational ground-state products, NO(upsilon=0)+N((4)S)+O((3)P), in about 45% of the cases. The internal product-state distribution of the NO fragment shows a similarity with the product-state distribution as predicted by the Franck-Condon overlap between a NO moiety of the dimer ion and a free NO. The dissociation dynamics seem to be independent of the NO internal energy. Finally, the dissociation dynamics reveal a correlation between the kinetic energy of the NO fragment and the degree of conservation of linear momentum between the O and N product atoms. The observations support a mechanism in which the recoil takes place along one of the NO bonds in the dimer.     

Dissociative recombination of electrons and molecular ions

The existing techniques for the calculation of the dissociative recombination (DR) of electrons and molecular ions were compared. The advantages of the method of multichannel quantum defect (MQD), in which equations are formulated directly for the T-matrix of collisions and the unitarity of the scattering S-matrix is thus ensured, were demonstrated. The effect of molecular rotation and of the nonadiabatic electron-rotation coupling on the e^– + H₂ ⁺ , H* + H reaction was investigated. A procedure was suggested based on the use of the adiabatic approximation (with respect to the nuclear rotation) in the near-threshold area while taking into account the contributions of the excited vibronic states of the Rydberg complex formed in an intermediate stage of the reaction. It is notable that the partial rate constants (and the corresponding cross-sections) arc very sensitive to the initial rotation excitation. However, the temperature-averaged rate constants under equilibrium conditions are only slightly affected by rotation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1336–1348, June, 1996.     

A spherical electron cloud hopping model for studying product branching ratios of dissociative recombination

A spherical electron cloud hopping (SECH) model is proposed to study the product branching ratios of dissociative recombination (DR) of polyatomic systems. In this model, the fast electron-captured process is treated as an instantaneous hopping of a cloud of uniform spherical fractional point charges onto a target M+q ion (or molecule). The sum of point charges (-1) simulates the incident electron. The sphere radius is determined by a critical distance (Rc eM) between the incoming electron (e-) and the target, at which the potential energy of the e(-)-M+q system is equal to that of the electron-captured molecule M+q(-1) in a symmetry-allowed electronic state with the same structure as M(+q). During the hopping procedure, the excess energies of electron association reaction are dispersed in the kinetic energies of M+q(-1) atoms to conserve total energy. The kinetic energies are adjusted by linearly adding atomic momenta in the direction of driving forces induced by the scattering electron. The nuclear dynamics of the resultant M+q(-1) molecule are studied by using a direct ab initio dynamics method on the adiabatic potential energy surface of M+q(-1), or together with extra adiabatic surface(s) of M+q(-1). For the latter case, the "fewest switches" surface hopping algorithm of Tully was adapted to deal with the nonadiabaticity in trajectory propagations. The SECH model has been applied to study the DR of both CH+ and H3O+(H2O)2. The theoretical results are consistent with the experiment. It was found that water molecules play an important role in determining the product branching ratios of the molecular cluster ion.     

Catalytic decomposition of dimethyl disulfide

We have studied dimethyl disulfide conversion on heterogeneous catalysts in a flow setup at T=250–350°C and atmospheric pressure. Methyl mercaptan appears to be the main reaction product. The rate of dimethyl disulfide decomposition and its selectivity towards methyl mercaptan in H₂S medium are higher than those in pure helium. Thus the process seems to involve the surface protons formed upon dissociative H₂S chemisorption.     

Catalytic synthesis of dimethyl sulfide from dimethyl disulfide and methanol

The reaction of dimethyl disulfide with methanol was studied at atmospheric pressure and temperature of 350°C in the presence of catalysts containing acid and basic sites.     

Methylation of benzene with dimethyl disulfide

Dimethyl disulfide reacts with benzene at 250–350°C over a period of 1–20 s in the presence of catalysts containing strong Brønsted and Lewis acid centers to give a mixture of methylbenzenes, viz. toluene, isomeric xylenes, mesitylene, and durene.     

Attachment cross sections of protonated water clusters

The attachment of water molecules onto size selected protonated water clusters has been experimentally investigated. Absolute attachment cross sections are measured as a function of cluster size, collision energy, and initial cluster temperature. Although thermal evaporation is ruled out in our experiment, attachment cross sections become significantly smaller than hard sphere cross sections as the collision energy increases. This feature is attributed to a transition from adiabatic to nonadiabatic regime. It is shown to be due to a dynamical effect: as the collision duration becomes shorter than the typical time required for collision energy redistribution into clusters internal energy, the attachment probability is reduced. We relate this typical time to the period of the main surface vibrational mode excited by the collisions. This hypothesis is further supported by results obtained with deuterated water clusters.     

Fragmentation cross sections of protonated water clusters

We have measured fragmentation cross sections of protonated water cluster cations (H(2)O)(n=30-50)H(+) by collision with water molecules. The clusters have well-defined sizes and internal energies. The collision energy has been varied from 0.5 to 300 eV. We also performed the same measurements on deuterated water clusters (D(2)O)(n=5-45)D(+) colliding with deuterated water molecules. The main fragmentation channel is shown to be a sequential thermal evaporation of single molecules following an initial transfer of relative kinetic energy into internal energy of the cluster. Unexpectedly, that initial transfer is very low on average, of the order of 1% of collision energy. We evaluate that for direct collisions (i.e., within the hard sphere radius), the probability for observing no fragmentation at all is more than 35%, independently of cluster size and collision energy, over our range of study. Such an effect is well known at higher energies, where it is attributed to electronic effects, but has been reported only in a theoretical study of the collision of helium atoms with sodium clusters in that energy range, where only vibrational excitation occurs.     

Dissociative recombination of electrons with molecular hydrogen ions

To a first approximation, the perturbation theory yields an explicit analytical expression for the cross section of the dissociative recombination of electrons with molecular hydrogen ions. The possible nonadiabatic transitions during the separation of the nuclei which lead to the appearance of H⁺+H^–, H(1s)+H(n=2), H(1s)+H(n=3) in finite reaction channels were considered. Numerical results are presented for the cross sections of direct and reverse reactions. The expression =4. 2 · 10^–8 T^–1/2 cm³/sec² was obtained for the recombination rate at low temperatures; this expression is in agreement with known results. Several general details of the calculation and their possible implications for the case of heavy molecular ions are discussed.     

Comparative study of measured and critically evaluated resonance integral to thermal cross section ratios,III

In the present paper, a tabulation is given of recommended Q₀-values [the ratio of the resonance integral (I₀) to the 2200 m·s^?1 cross-section (δ₀)] for 107 (n, γ) reactions of interest in NAA, including a revision and updating of formerly published results for 57 isotopes. The values were either critically evaluated from literature, or-in the majority of cases — experimentally determined according to the Cd-ratio method, with a correction for a non-ideal epithermal neutron flux distribution. These Q₀-measurements were performed at INW, Gent, at KFKI, Budapest, and occasionally at Risø. A comparison is made with results obtained by other workers or with values derived from δ₀'s and I₀'s quoted in recent compilations.     

Activity of catalysts in the synthesis of dimethyl sulfide from dimethyl disulfide

Dimethyl disulfide conversion at T = 190–350°C over catalysts containing acid and basic sites is reported. The products of this reaction are dimethyl sulfide, methanethiol, hydrogen sulfide, carbon disulfide, methane, and ethylene. At 190°C, these products form via parallel reactions. At higher temperature of up to 350°C, dimethyl sulfide can form by the condensation of the resulting methanethiol. The strong basic sites of the catalysts are uninvolved in dimethyl sulfide formation. Over catalysts whose surface has only strong protonic or strong Lewis acid sites, dimethyl sulfide formation does take place, but slowly and nonselectively. The highest dimethyl sulfide formation activity and selectivity are shown by catalysts having medium-strength basic sites along with strong protonic and strong Lewis acid sites.