Anisotropic fragmentation in low-energy dissociative recombination
S. Novotny, H. Rubinstein, H. Buhr, O. Novotný, J. Hoffmann, M. B. Mendes, D. A. Orlov, M. H. Berg, M. Froese, A. S. Jaroshevich, B. Jordon-Thaden, C. Krantz, M… 展开作者
S. Novotny, H. Rubinstein, H. Buhr, O. Novotný, J. Hoffmann, M. B. Mendes, D. A. Orlov, M. H. Berg, M. Froese, A. S. Jaroshevich, B. Jordon-Thaden, C. Krantz, M. Lange, M. Lestinsky, A. Petrignani, I. F. Schneider, D. Shafir, F. O. Waffeu Tamo, D. Zajfman, D. Schwalm, A. Wolf
备注：
8 pages, 4 figures; The Article will be published in the proceedings of DR 2007, a symposium on Dissociative Recombination held in Ameland, The Netherlands (18.-23. July 2008); Reference 19 has been published meanwhile in S. Novotny, PRL 100, 193201 (2008)
On a dense energy grid reaching up to 75 meV electron collision energy the fragmentation angle and the kinetic energy release of neutral dissociative recombination fragments have been studied in a twin merged beam experiment. The anisotropy described by Legendre polynomials and the extracted rotational state contributions were found to vary on a likewise narrow energy scale as the rotationally averaged rate coefficient. For the first time angular dependences higher than 2$^{nd}$ order could be deduced. Moreover, a slight anisotropy at zero collision energy was observed which is caused by the flattened velocity distribution of the electron beam.
We present a simple two-dimensional model of the indirect dissociative recombination process. The model has one electronic and one nuclear degree of freedom and it can be solved to high precision, without making any physically motivated approximations, by employing the exterior complex scaling method together with the finite-elements method and discrete variable representation. The approach is applied to solve a model for dissociative recombination of H$_2^+$ and the results serve as a benchmark to test validity of several physical approximations commonly used in the computational modeling of …
The cross section for dissociative recombination of BeH^+ is calculated by solution of the time-dependent Schrodinger equation in the local complex potential approximation. The effects of couplings between resonant states and the Rydberg states converging to the ground state of the ion are studied. The relevant potentials, couplings and autoionization widths are extracted using ab initio electron scattering and structure calculations, followed by a diabatization procedure. The calculated cross sections shows a sizable magnitude at low energy, followed by a high-energy peak centered around 1 eV…
A theoretical description of the dissociative recombination process for the HCO+ ion suggests that the nonadiabatic Renner-Teller coupling between electronic and vibrational degrees of freedom plays an important role. This finding is consistent with a recent study of this process for another closed-shell molecule, the H3+ ion, where Jahn-Teller coupling was shown to generate a relatively high rate. The cross section obtained here for the dissociative recombination of HCO+exhibits encouraging agreement with a merged-beam experiment.
A general first-principles theory of dissociative recombination is developed for highly-symmetric molecular ions and applied to H$_3$O$^{+}$ and CH$_3^+$, which play an important role in astrophysical, combustion, and laboratory plasma environments. The theoretical cross-sections obtained for the dissociative recombination of the two ions are in good agreement with existing experimental data from storage ring experiments.
This paper reports results from an experimental investigation of the dissociative recombination (DR) of the helium dimer ions at the heavy-ion Test Storage Ring (TSR) in Heidelberg, observing neutral products from electron-ion collisions in a merged beams configuration at relative energies from near-zero (thermal electron energy about 10 meV) up to 40 eV.
The collision-energy resolved rate coefficient for dissociative recombination of HD+ ions in the vibrational ground state is measured using the photocathode electron target at the heavy-ion storage ring TSR. Rydberg resonances associated with ro-vibrational excitation of the HD+ core are scanned as a function of the electron collision energy with an instrumental broadening below 1 meV in the low-energy limit. The measurement is compared to calculations using multichannel quantum defect theory, accounting for rotational structure and interactions and considering the six lowest rotational energy…
Cross sections and thermal rate coefficients are computed for electron-impact dissociative recombination and vibrational excitation/de-excitation of the N$^+_2$ molecular ion in its lowest six vibrational levels, for collision energies/temperatures up to 2.3 eV/5000 K.
We used the multichannel quantum defect theory to compute cross sections and rate coefficients for the dissociative recombination of CH$^+$ initially in its lowest vibrational level $v_i^+ = 0$ with electrons of incident energy bellow $0.2$ eV. We have focused on the contribution of the $2$ $^2Π$ state which is the main dissociative recombination route at low collision energies. The final cross section is obtained by averaging the relevant initial rotational states $(N_i^+ = 0,\dots,10)$ with a $300$ K Boltzmann distribution.The Maxwell isotropic rate coefficients for dissociative recombinatio…
Rate coefficients for dissociative recombination and state-to-state rotational transitions of the D$_{2}^{+}$ ion induced by collisions with very low-energy electrons have been reported following our previous studies on HD$^{+}$ and H$_{2}^{+}$ [9,10]. The same molecular structure data sets, excitations ($N_{i}^{+} \rightarrow$ $N_{f}^{+}=N_{i}^{+}+2$ for $N_{i}^{+}=0$ to $10$) and de-excitations ($N_{i}^{+}$ $\rightarrow$ $N_{f}^{+}=N_{i}^{+}-2$, for $N_{i}^{+}=2$ to $10$) were used for collision energies ranging from $0.01$ meV to $0.3$ eV. Isotopic effects for dissociative recombination and…
The dissociative recombination of the lowest rotational states of H3+ has been investigated at the storage ring TSR using a cryogenic 22-pole radiofrequency ion trap as injector. The H3+ was cooled with buffer gas at ~15 K to the lowest rotational levels, (J,G)=(1,0) and (1,1), which belong to the ortho and para proton-spin symmetry, respectively. The rate coefficients and dissociation dynamics of H3+(J,G) populations produced with normal- and para-H2 were measured and compared to the rate and dynamics of a hot H3+ beam from a Penning source. The production of cold H3+ rotational populations w…
We report measurements on the H$^{+}$ + H$^{+}$ fragmentation channel following direct single-photon double ionization of neutral NH$_{3}$ at 61.5 eV, where the two photoelectrons and two protons are measured in coincidence using 3-D momentum imaging. We identify four dication electronic states that contribute to H$^{+}$ + H$^{+}$ dissociation, based on our multireference configuration-interaction calculations of the dication potential energy surfaces. The extracted branching ratios between these four dication electronic states are presented. Of the four dication electronic states, three disso…
New high-resolution dissociative recombination rate coefficients of rotationally cool and hot H3+ in the vibrational ground state have been measured with a 22-pole trap setup and a Penning ion source, respectively, at the ion storage ring TSR. The experimental results are compared with theoretical calculations to explore the dependence of the rate coefficient on ion temperature and to study the contributions of different symmetries to probe the rich predicted resonance spectrum. The break-up energy was investigated by fragment imaging to derive internal temperatures of the stored parent ions u…
Cross sections are presented for dissociative recombination and electron-impact vibrational excitation of the ArH+ molecular ion at electron energies appropriate for the interstellar environment. The R-matrix method is employed to determine the molecular structure data, i.e. the position and width of the resonance states. The cross sections and the corresponding Maxwellian rate coefficients are computed using a method based on the Multichannel Quantum Defect Theory. The main result of the paper is the very low dissociative recombination rate found at temperatures below 1000K. This is in agreem…
The article presents calculated dissociative recombination (DR) rate coefficients for H+3 . The previous theoretical work on H+3 was performed using the adiabatic hyperspherical approximation to calculate the target ion vibrational states and it considered just a limited number of ionic rotational states. In this study, we use accurate vibrational wave functions and a larger number of possible rotational states of the H3+ ground vibrational level. The DR rate coefficient obtained is found to agree better with the experimental data from storage-ring experiments than the previous theoretical cal…
Theoretical study of the excited states of NeH and of their non-adiabiatic couplings: a preliminary for the modeling of the dissociative recombination of NeH+
We have investigated dissociative recombination (DR) of NH$^+$ with electrons using a merged beams configuration at the TSR heavy-ion storage ring located at the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. We present our measured absolute merged beams recombination rate coefficient for collision energies from 0 to 12 eV. From these data we have extracted a cross section which we have transformed to a plasma rate coefficient for the collisional plasma temperature range from $T_{\rm pl} = 10$ to $18000$ K. We show that the NH$^+$ DR rate coefficient data in current astrochem…
We have measured dissociative recombination of HCl+ with electrons using a merged beams configuration at the heavy-ion storage ring TSR located at the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. We present the measured absolute merged beams recombination rate coefficient for collision energies from 0 to 4.5 eV. We have also developed a new method for deriving the cross section from the measurements. Our approach does not suffer from approximations made by previously used methods. The cross section was transformed to a plasma rate coefficient for the electron temperature ra…
We have developed a theoretical method for interpretation of photoionization experiments with the H_3 molecule. In the present study we give a detailed description of the method, which combines multichannel quantum defect theory, the adiabatic hyperspherical approach, and the techniques of outgoing Siegert pseudostates. The present method accounts for vibrational and rotation excitations of the molecule, deals with all symmetry restrictions imposed by the geometry of the molecule, including vibrational, rotational, electronic and nuclear spin symmetries. The method was recently applied to trea…
We report on the fragmentation of the water molecule by $1$ MeV H$^{+}$, He$^{+}$ and 650 keV N$^{+}$ ion impact. The fragment-ion energy spectra were measured by an electrostatic spectrometer at different observation angles. The obtained double-differential fragmentation cross sections for N$^{+}$ is found to be more than an order of magnitude higher, than that for H$^{+}$. The relative ratios of the fragmentation channels are also different for the three projectiles. Additional fragmentation channels were observed in the spectra for He$^{+}$ and for N$^{+}$ impact, which are missing in the c…
Molecular fragmentation leading to the formation of negatively and positively charged hydrogen ions in 7-keV OH$^+$ + Ar collisions is investigated experimentally. The most striking finding is that negative and positive hydrogen ions are emitted with very similar angular dependences. Also, the kinetic energy distribution of the H$^+$ fragment shows strong similarities with that of the ejected H$^-$ ion. The kinematics of the emitted H core is found to be essentially driven by its scattering on the atomic target. However, in addition to this binary-encounter process, dissociative electronic exc…
To describe multiple interacting fragmentation continua, we develop a method in which the vibrational channel functions obey outgoing wave Siegert boundary conditions. This paper demonstrates the utility of the Siegert approach, which uses channel energy eigenvalues that possess a negative imaginary part. The electron scattering energy in each such channel is rotated upward, giving it an equal and opposite imaginary part. This permits a natural inclusion of vibrational continua without requiring them to appear as explicit channels in the scattering matrix. Calculations illustrate the applicati…
We present a study of multiphoton dissociative ionization from molecules. By solving the time-dependent Schrödinger equation for H$_2^+$ and projecting the solution onto double continuum scattering states, we observe the correlated electron-nuclear ionization dynamics in detail. We show --- for the first time --- how multiphoton structure prevails as long as the energies of all fragments are accounted for. Our current work provides a new avenue to analyze strong-field fragmentation that leads to a deeper understanding of the correlated molecular dynamics.
We report experimental results on three-dimensional momentum imaging measurements of anions generated via dissociative electron attachment to gaseous formamide. From the momentum images, we analyze the angular and kinetic energy distributions for NH$_2^{-}$, O$^{-}$, and H$^{-}$ fragments and discuss the possible electron attachment and dissociation mechanisms for multiple resonances for two ranges of incident electron energies, from 5.3~eV to 6.8~eV, and from 10.0~eV to 11.5~eV. {\it Ab initio} theoretical results for the angular distributions of the NH$_2^{-}$ anion for $\sim$6~eV incident e…
We review the study of dissociative recombination and ro-vibrational excitation of diatomic and small polyatomic molecular ions initiating complex organic molecules formation. In particular, we show how Multichannel Quantum Defect Theory (MQDT) and R-matrix methods are used to compute cross sections and rate coefficients for cations in well defined ro-vibrational levels of the ground electronic state, from sub-meV up to few eV collision energies. The most recent MQDT results are compared with either other theoretical data, or with measured data obtained in storage-ring experiments.
We report on the fragmentation dynamics of triply charged, diatomic, molecular ions of NO and CO. Dissociative fragmentation after multiple ionization of NO and CO is studied under the impact of 200 keV proton beam using recoil-ion momentum spectrometer. Kinetic Energy Release distributions (KERDs) for various fragmentation channels were obtained. We have also calculated the potential energy curves (PECs) for ground and several excited states of NO^{3+} and CO^{3+} molecular ion. The obtained KERDs are discussed in the background of the calculated PECs as well as the simple Coulomb excitation …
Study of low-energy electron-induced dissociation of 1-Propanol
Indian Institute of Science Education and Research Kolkata（印度科学教育研究所加尔各答分校）；J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences（捷克科学院 J. 赫鲁霍夫斯基物理化学研究所）；Center for Atomic, Molecular and Optical Sciences and Technologies, Joint initiative of IIT Tirupati and IISER Tirupati（提鲁帕蒂原子、分子与光学科学与技术中心（提鲁帕蒂理工学院与印度科学教育研究所提鲁帕蒂分校联合倡议））
We study the electron-impact induced ionization of O$_{2}$ from threshold to 120 eV using the electron spectroscopy method. Our approach is simple in concept and embodies the ion source with a collision chamber and a mass spectrometer with a quadruple filter as a selector for the product ions. The combination of these two devices makes it possible to unequivocally collect all energetic fragment ions formed in ionization and dissociative processes and to detect them with known efficiency. The ion source allows to vary and tune the electron-impact ionization energy and the target-gas pressure. W…
We describe the major low-energy electron-impact processes involving H$^+_2$ and HD$^+$, relevant for the astrochemistry of the early Universe: Dissociative recombination, elastic, inelastic and superelastic scattering. We report cross sections and Maxwellian rate coefficients of both rotational and vibrational transitions, and outline several important features, like isotopic, rotational and resonant effects.
Strong Evidence for Formation of Hydroxyl Anion via 2-Particle-1-Hole Feshbach Resonances
Indian Institute of Science Education and Research Kolkata（印度科学教育研究学院加尔各答分校）；Ashoka University（阿肖卡大学）；Institute of Physical Chemistry, Polish Academy of Sciences（波兰科学院物理化学研究所）；University of Kassel（卡塞尔大学）；Center for Atomic, Molecular and Optical Sciences and Technologies, Joint initiative of IIT Tirupati and IISER Tirupati（原子、分子和光学科学与技术中心（泰米尔纳德邦理工学院与泰米尔纳德邦科学教育研究学院联合倡议））
Rate coefficients for the dissociative recombination, vibrational excitation and vibrational de-excitation of the BeT$^{+}$ ion for all vibrational levels of its ground electronic state ($ X\ensuremath{^{1}Σ^{+}},v_{i}^{+}=0,\dots,27$) are reported, including in the calculation the contribution of super-excited states of the BeT complex pertaining to three electronic symmetries - $^{2}Π$, $^{2}Σ^{+}$, and $^{2}Δ$. These data are suitable for the kinetic modeling of beryllium and tritium containing plasma, as encountered in magnetic fusion devices with beryllium walls (JET, ITER). In the presen…
