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We investigate the harmonic response of neon atoms to mid-IR laser fields (2000-3000nm) using a single-active electron (SAE) model and the fully ab initio all-electron R-Matrix with Time-dependence (RMT) method. The laser peak intensity and wavelength are varied to find suitable parameters for high-harmonic imaging in the water window. Comparison of the SAE and RMT results shows qualitative agreement between them as well as parameters such as the cutoff frequency predicted by the classical three-step model. However, there are significant differences in the details, particularly in the predicted conversion efficiency. These details indicate the possible importance of multi-electron effects, as well as a strong sensitivity of quantitative predictions on specific aspects of the numerical model.

Half-cycle oscillation is observed in transient absorption spectra of N2O at N K edge (400 eV) irradiated by intense IR pulses, which is attributed to tunneling ionization of core excited states by intensive TDSE-based simulation.

We consider few-photon ionization of atomic lithium by linearly polarized femtosecond laser pulses, and demonstrate that asymmetries of the electron angular distribution can occur for initially polarized (2p, m=+1) target atoms. The dependence of the photoelectron emission angle relative to the electric field direction is investigated at different laser intensities and wavelengths. The experimental spectra show excellent agreement with numerical solutions of the time-dependent Schroedinger equation. In the perturbative picture, the angular shift is traced back to interferences between partial waves with mean magnetic quantum number $\ne$0. This observation allows us to obtain quantum mechanical information on the electronic final state., Comment: 7 pages, 4 figures

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., Comment: 20 pages, 13 figures

A common way to evaluate electronic integrals for polyatomic molecules is to use Becke’s partitioning scheme (Becke and Chem, 1988) in conjunction with overlapping grids centered at each atomic site. The Becke scheme was designed for integrands that fall off rapidly at large distances, such as those approximating bound electronic states. When applied to states in the electronic continuum, however, Becke scheme exhibits slow convergence and it is highly redundant. Here, we present a modified version of Becke scheme that is applicable to functions of the electronic continuum, such as those involved in molecular photoionization and electron–molecule scattering, and which ensures convergence and efficiency comparable to those realized in the calculation of bound states. In this modified scheme, the atomic weights already present in Becke’s partition are smoothly switched off within a range of few bond lengths from their respective nuclei, and complemented by an asymptotically unitary weight. The atomic integrals are evaluated on small spherical grids, centered on each atom, with size commensurate to the support of the corresponding atomic weight. The residual integral of the interstitial and long-range region is evaluated with a central master grid. The accuracy of the method is demonstrated by evaluating integrals involving integrands containing Gaussian Type Orbitals and Yukawa potentials , on the atomic sites, as well as spherical Bessel functions centered on the master grid. These functions are representative of those encountered in realistic electron-scattering and photoionization calculations in polyatomic molecules.

Attosecond photoionization time delays reveal information about the potential energy landscape that an outgoing electron wavepacket probes upon ionization. In this study, we experimentally quantify the dependence of the time delay on the angular momentum of the liberated photoelectrons. For this purpose, we resolved electron quantum-path interference spectra in energy and angle using a two-color attosecond pump–probe photoionization experiment in helium. A fitting procedure of the angle-dependent interference pattern allows us to disentangle the relative phase of all four quantum pathways that are known to contribute to the final photoelectron signal. In particular, we resolve the dependence on angular momentum of the delay of one-photon transitions between continuum states, which is an essential and universal contribution to the total photoionization delay observed in attosecond pump–probe measurements. For such continuum–continuum transitions, we measure a delay between outgoing s and d electrons as large as 12 attoseconds, close to the ionization threshold in helium. Both single-active-electron and first-principles ab initio simulations confirm this observation for helium and hydrogen, demonstrating the universality of the observed delays., Optica, 7 (2), ISSN:2334-2536

We demonstrate that the beating between 1- and 2-photon-transitions enables a sensitive detection of high-order phase terms of electron wave packets. This allows us to observe phase features well beyond the capabilities of existing attosecond spectroscopy.

Coherent control of the photoelectron angular distribution (PAD) in ionization by a bichromatic circularly polarized field is theoretically studied in neon in the photon energy range 16--20 eV. The breakdown of the PAD axial symmetry with respect to the light propagation direction is analyzed. The coherent control of the PAD manifests itself through: (1) a change from a one-lobe to a three-lobe shape, respectively, for co- and counter-rotating harmonics, (2) a variation of the polar asymmetry with the light frequency, and (3) a rotation of the PAD around the direction of the beam depending on the relative phase between the harmonics. Tuning the lowest harmonic at the $2{p}^{5}3s$ or $2{p}^{5}4s$ intermediate excited states strongly influences the PAD. In contrast to atomic hydrogen and the alkali atoms, the cases of equal and opposite helicity are not related in neon. Features of a conjugate polarization setup, when one harmonic is linearly polarized while the other one is circularly polarized, are also discussed.

The tunnelling of a particle through a potential barrier is a key feature of quantum mechanics that goes to the core of wave–particle duality. The phenomenon has no counterpart in classical physics, and there are no well constructed dynamical observables that could be used to determine ‘tunnelling times’. The resulting debate1–5 about whether a tunnelling quantum particle spends a finite and measurable time under a potential barrier was reignited in recent years by the advent of ultrafast lasers and attosecond metrology6. Particularly important is the attosecond angular streaking (‘attoclock’) technique7, which can time the release of electrons in strong-field ionization with a precision of a few attoseconds. Initial measurements7–10 confirmed the prevailing view that tunnelling is instantaneous, but later studies11,12 involving multi-electron atoms—which cannot be accurately modelled, complicating interpretation of the ionization dynamics—claimed evidence for finite tunnelling times. By contrast, the simplicity of the hydrogen atom enables precise experimental measurements and calculations13–15 and makes it a convenient benchmark. Here we report attoclock and momentum-space imaging16 experiments on atomic hydrogen and compare these results with accurate simulations based on the three-dimensional time-dependent Schrodinger equation and our experimental laser pulse parameters. We find excellent agreement between measured and simulated data, confirming the conclusions of an earlier theoretical study17 of the attoclock technique in atomic hydrogen that presented a compelling argument for instantaneous tunnelling. In addition, we identify the Coulomb potential as the sole cause of the measured angle between the directions of electron emission and peak electric field: this angle had been attributed11,12 to finite tunnelling times. We put an upper limit of 1.8 attoseconds on any tunnelling delay, in agreement with recent theoretical findings18 and ruling out the interpretation of all commonly used ‘tunnelling times’19 as ‘time spent by an electron under the potential barrier’20. Simulation and measurement of the photoionization of atomic hydrogen at attosecond resolution confirm that the tunnelling of the ejected electron is instantaneous.

Two-color XUV plus near-IR multiphoton ionization of the helium ion by circularly polarized light is studied in the vicinity of the 3p resonance. Combining the analysis of results obtained by solving the time-dependent Schrodinger equation and that of the quasienergy spectrum of He+ reveals the physical mechanisms that determine the photoelectron spectra and the variation of the circular dichroism as a function of the near-IR intensity.

The presumed connection in attoclock setups between the electron tunneling time and its asymptotic momentum has triggered vigorous debates. In neutral atomic systems investigated so far, the action of the long-range Coulomb potential on the electron momentum hinders extracting the effect of the tunneling process on the offset angle of the asymptotic electron momentum. We propose and investigate an attoclock experiment using ${\mathrm{F}}^{\ensuremath{-}}$ or ${\mathrm{Cl}}^{\ensuremath{-}}$ to circumvent this difficulty. Our calculations, performed with realistic laser parameters in the tunneling regime, could be checked directly against experiment and predict essentially a ``zero'' offset angle with no detectable effect of polarization.

We propose an attosecond XUV-pump IR-probe photoionization protocol that employs pairs of counter-rotating consecutive harmonics and angularly resolved photoelectron detection, thereby providing direct measurement of ionization phases. The present method, which we call circular holographic ionization-phase meter (CHIP), gives also access to the phase of photoemission amplitudes of even-parity continuum states from a single time-delay measurement, since the relative phase of one- and two-photon ionization pathways is imprinted in the photoemission anisotropy. The method is illustrated with \emph{ab initio} simulations of photoionization via autoionizing resonances in helium. The rapid phase excursion in the transition amplitude to both the dipole-allowed $(2s2p)^1$P$^{\rm o}$ and the dipole-forbidden $(2p^2)^1$D$^{\rm e}$ states are faithfully reproduced., Comment: 6 pages, 5 figures

Synopsis Circular dichroism in the two-color XUV + IR ionization of He+ is considered theoretically in connection with the recent experiment by Ilchen et al. [1]. The sharp decrease of the circular dichroism with increasing intensity of the IR field when the XUV frequency is near the 1s – 3p resonant excitation is studied. It is confirmed that the main source of the effect is the axial component of the polarizability, which has opposite signs for magnetic substates with opposite projections.

The complex Kohn variational method is extended to compute light-driven electronic transitions between continuum wave functions in atomic and molecular systems. This development enables the study of multiphoton processes in the perturbative regime for arbitrary light polarization. As a proof of principle, we apply the method to compute the photoelectron spectrum arising from the pump--probe two-photon ionization of helium induced by a sequence of extreme ultraviolet and infrared light pulses. We compare several two-photon ionization pump--probe spectra, resonant with the ($2s2p)\phantom{\rule{0.16em}{0ex}}^{1}P_{1}^{o}$ Feshbach resonance, with independent simulations based on the atomic B-spline close-coupling stock code, and find good agreement between the two approaches. This finite-pulse perturbative approach is a step towards the ab initio study of weak-field attosecond processes in polyelectronic molecules.

Progress in high-harmonic generation has led to high-energy attosecond pulses with cutoff above the carbon $1s$ edge (283.8 eV). These pulses are essential to extend time-resolved spectroscopies to the water window in order to control electron dynamics in solvated organic species. Here we report a step towards this goal: the measurement, with subcycle time resolution, of the attosecond transient absorption spectrum of argon at the $2{p}^{\ensuremath{-}1} {L}_{2,3}$ edge ($\ensuremath{\sim}250$ eV) in the presence of a short-wave infrared control pulse. The measurements, supported by theoretical simulations, demonstrate the concurrent role of Auger decay and tunnel ionization in the driven evolution of inner-valence holes of polyelectronic atoms.

We present an experimental investigation of attosecond transient absorption spectroscopy near the L 2 , 3 -edge of argon gas by using an attosecond pulse in the 240-250 eV range.

The seeded Free-Electron Laser (FEL) FERMI is the first source of short-wavelength light possessing the full coherence of optical lasers, together with the extreme power available from FELs. FERMI provides longitudinally coherent radiation in the Extreme Ultraviolet and soft x-ray spectral regions, and therefore opens up wide new fields of investigation in physics. We first propose experiments exploiting this property to provide coherent control of the photoionization of neon and helium, carry out numerical calculations to find optimum experimental parameters, and then describe how these experiments may be realized. The approach uses bichromatic illumination of a target and measurement of the products of the interaction, analogous to previous Brumer-Shapiro-type experiments in the optical spectral range. We describe operational schemes for the FERMI FEL, and simulate the conditions necessary to produce light at the fundamental and second or third harmonic frequencies, and to control the phase with respect to the fundamental. We conclude that a quantitative description of the phenomena is extremely challenging for present state-of-the-art theoretical and computational methods, and further development is necessary. Furthermore, the intensity available may already be excessive for the experiments proposed on helium. Perspectives for further development are discussed.

Recent attoclock experiments and theoretical studies regarding the strong-field ionization of atoms by few-cycle infrared pulses revealed new features that have attracted much attention. Here we investigate tunneling ionization and the dynamics of the electron probability using Bohmian Mechanics. We consider a one-dimensional problem to illustrate the underlying mechanisms of the ionization process. It is revealed that in the major part of the below-the-barrier ionization regime, in an intense and short infrared pulse, the electron does not tunnel \through" the entire barrier, but rather already starts from the classically forbidden region. Moreover, we highlight the correspondence between the probability of locating the electron at a particular initial position and its asymptotic momentum. Bohmian Mechanics also provides a natural definition of mean tunneling time and exit position, taking account of the time dependence of the barrier. Finally, we find that the electron can exit the barrier with significant kinetic energy, thereby corroborating the results of a recent study [Camus et al., Phys. Rev. Lett. 119 (2017) 023201].

The tunnelling of a particle through a potential barrier is a key feature of quantum mechanics that goes to the core of wave-particle duality. The phenomenon has no counterpart in classical physics, and there are no well constructed dynamical observables that could be used to determine 'tunnelling times'. The resulting debate

We investigate the coherent control of the photo\-electron angular distribution in bichromatic atomic ionization. Neon is selected as target since it is one of the most popular systems in current gas-phase experiments with free-electron lasers (FELSs). In particular, we tackle practical questions, such as the role of the fine-structure splitting, the pulse length, and the intensity. Time-dependent and stationary perturbation theory are employed, and we also solve the time-dependent Schr\"odinger equation in a single-active electron model. We consider neon ionized by a FEL pulse whose fundamental frequency is in resonance with either $2p-3s$ or $2p-4s$ excitation. The contribution of the non\-resonant two-photon process and its potential constructive or destructive role for quantum coherent control is investigated., Comment: 10 pages, 6 figures

Physical review letters 118(1), 013002 (2017). doi:10.1103/PhysRevLett.118.013002, Intense, circularly polarized extreme-ultraviolet and near-infrared (NIR) laser pulses are combined to double ionize atomic helium via the oriented intermediate He+(3p) resonance state. Applying angle-resolved electron spectroscopy, we find a large photon helicity dependence of the spectrum and the angular distribution of the electrons ejected from the resonance by NIR multiphoton absorption. The measured circular dichroism is unexpectedly found to vary strongly as a function of the NIR intensity. The experimental data are well described by theoretical modeling and possible mechanisms are discussed., Published by APS, College Park, Md.

In this Letter, the statement 'I.I. and A.B. performed computations at the NCI Australia' was missing from the Acknowledgements section. This has been corrected online.

We analyze the photoelectron angular distribution in two-pathway interference between non\-resonant one-photon and resonant two-photon ionization of neon. We consider a bichromatic femtosecond XUV pulse whose fundamental frequency is tuned near the $2p^5 3s$ atomic states of neon. The time-dependent Schr\"odinger equation is solved and the results are employed to compute the angular distribution and the associated anisotropy parameters at the main photoelectron line. We also employ a time-dependent perturbative approach, which allows obtaining information on the process for a large range of pulse parameters, including the steady-state case of continuous radiation, i.e., an infinitely long pulse. The results from the two methods are in relatively good agreement over the domain of applicability of perturbation theory.

We discuss symmetry properties of a quantum system comprised of four identical atoms in different large - distance molecular configurations and derive general selection rules with possible nuclei exchange after a four-atom collision, e.g. a molecular reaction. We focus on the following important collisional processes: (1) two bound diatomic molecules, (2) a bound triatomic molecule and a free atom, and (3) a bound diatomic molecule and two free atoms. The approach employed to treat this problem is based on analyzing eigenspaces of the large-distance Hamiltonians and the corresponding constants of motion. The symmetry is then studied by decomposing a given eigenspace of the large-distance Hamiltonian in irreducible representations of the complete nuclear permutation inversion group G 48 of four identical nuclei appropriate for short distances using appropriate symmetry subgroups. The final results provide selection rules for collisions of four identical atoms.

The photodetachment cross sections of the C2H− and C4H− molecular anions in their ground electronic and vibrational states are determined using the R-matrix approach. The obtained results are compared with available experimental data of absolute photodetachment cross sections. In addition, cross sections for the inverse process, i.e., radiative electron attachment, have also been determined and are used to obtain the corresponding thermally-averaged rate coefficients. At a temperature of 300 K, the rate coefficients are 2.3 × 10-16 and 18 × 10-16 cm3/s for C2H− and C4H−, respectively.

The existence of negative ions in interstellar clouds has been associated for several decades with the process of radiative electron attachment. In this Letter, we report compelling evidence supporting the fact that the radiative attachment of a low-energy electron is inefficient to form the carbon chain anions CN^{-}, C_{3}N^{-}, and C_{5}N^{-} detected in interstellar clouds. The validity of the approach is confirmed by good agreement with experimental data obtained for the inverse photodetachment process, which represents the major cause of anion destruction in interstellar space. As a consequence, we suggest alternative models that could explain the formation of anions.

The existence of negative ions in interstellar clouds has been associated for several decades with the process of radiative electron attachment. In this Letter, we report compelling evidence supporting the fact that the radiative attachment of a low-energy electron is inefficient to form the carbon chain anions CN^{-}, C_{3}N^{-}, and C_{5}N^{-} detected in interstellar clouds. The validity of the approach is confirmed by good agreement with experimental data obtained for the inverse photodetachment process, which represents the major cause of anion destruction in interstellar space. As a consequence, we suggest alternative models that could explain the formation of anions.

We investigate two-pathway interferences between nonresonant one-photon and resonant two-photon ionization of atomic hydrogen. In particular, we analyze in detail the photoionization mediated by the fundamental frequency and the second harmonic of a femtosecond VUV pulse when the fundamental is tuned near an intermediate atomic state. Following our recent study [Phys. Rev. A 91, 063418 (2015)PLRAAN1050-294710.1103/PhysRevA.91.063418] of such effects with linearly polarized light, we analyze a similar situation with circularly polarized radiation. As a consequence of the richer structure in circularly polarized light, characterized by its right-handed or left-handed helicity, we present and discuss various important features associated with the photoelectron angular distribution.

Researchers demonstrate correlation of two colours (63.0 and 31.5 nm wavelengths) in a free-electron laser and control photoelectron angular distribution by adjusting phase with 3 attosecond resolution. Extreme ultraviolet and X-ray free-electron lasers (FELs) produce short-wavelength pulses with high intensity, ultrashort duration, well-defined polarization and transverse coherence, and have been utilized for many experiments previously possible only at long wavelengths: multiphoton ionization1, pumping an atomic laser2 and four-wave mixing spectroscopy3. However one important optical technique, coherent control, has not yet been demonstrated, because self-amplified spontaneous emission FELs have limited longitudinal coherence4,5,6,7. Single-colour pulses from the FERMI seeded FEL are longitudinally coherent8,9, and two-colour emission is predicted to be coherent. Here, we demonstrate the phase correlation of two colours, and manipulate it to control an experiment. Light of wavelengths 63.0 and 31.5 nm ionized neon, and we controlled the asymmetry of the photoelectron angular distribution10,11 by adjusting the phase, with a temporal resolution of 3 as. This opens the door to new short-wavelength coherent control experiments with ultrahigh time resolution and chemical sensitivity.

We consider the ionization of neon induced by a femtosecond laser pulse composed of overlapping, linearly polarized bichromatic extreme ultraviolet and infrared fields. In particular, we study the effects of infrared light on a two-pathway ionization scheme for which Ne $2{s}^{2}2{p}^{5}3s\phantom{\rule{0.16em}{0ex}}^{1}P$ is used as the intermediate state. Using time-dependent calculations, supported by a theoretical approach based on the strong-field approximation, we analyze the ionization probability and the photoelectron angular distributions associated with the different sidebands of the ionization spectrum. Complex oscillations of the angular distribution anisotropy parameters as a function of the infrared light intensity are revealed. Finally, we demonstrate that coherent control of the asymmetry is achievable by tuning the infrared frequency to a nearby electronic transition.

We discuss exciting recent progress in the theoretical description of molecular ion dissociative recombination, with further applications to related processes such as molecular photoionization and rovibrationally-inelastic electron collisions with molecular ions. The techniques are based on quantum defect theory, an efficient tool for characterizing electron–ion collision processes, and on a generalized adiabatic formulation. When needed, the approximation of adiabaticity in the dissociative coordinate is lifted by taking non-adiabatic couplings explicitly into account. We concentrate on a time-independent theoretical framework that has been applied to describe dissociative recombination in ions such as H 3 + , its isotopologues (H 2 D + , D 2 H + and D 3 + ), and HCO + (DCO + ).

We present a combined experimental and theoretical investigation of the dynamics and angular dependence of dissociative electron attachment to methane. We show that a triply degenerate (T2) Feshbach resonance is responsible for the broad 10 eV dissociation peak in methane. This resonance alone is shown to correlate asymptotically to the various dissociation channels observed experimentally. The molecular-frame entrance amplitude for electron attachment is calculated for each component of the threefold degenerate resonance. By investigating the topology of the anion potential energy surfaces, we deduce the main pathways to two- and three-body breakup channels involving both bond scission and bond formation. The computed fragment angular distributions reproduce the main trends of the experimental measurements.

A first-principle theoretical approach to study the process of radiative electron attachment is developed and applied to the negative molecular ions CN(-), C4H(-), and C2H(-). Among these anions, the first two have already been observed in the interstellar space. Cross sections and rate coefficients for formation of these ions by direct radiative electron attachment to the corresponding neutral radicals are calculated. For the CN molecule, we also considered the indirect pathway, in which the electron is initially captured through non-Born-Oppenheimer coupling into a vibrationally resonant excited state of the anion, which then stabilizes by radiative decay. We have shown that the contribution of the indirect pathway to the formation of CN(-) is negligible in comparison to the direct mechanism. The obtained rate coefficients for the direct mechanism at 30 K are 7 × 10(-16) cm(3)/s for CN(-), 7 × 10(-17) cm(3)/s for C2H(-), and 2 × 10(-16) cm(3)/s for C4H(-). These rates weakly depend on temperature between 10 K and 100 K. The validity of our calculations is verified by comparing the present theoretical results with data from recent photodetachment experiments.

We consider the effect of substituting atomic ligands $X$ with different electronic properties in the carbon-$K$-shell photoionization of the linear $X\mathrm{CC}X$ molecules. We study the cases of lithium, hydrogen, and fluorine as ligands bonded to the carbon atoms. The molecular frame photoelectron angular distributions are computed using the variational complex Kohn technique. The electronic properties of the ligands have direct observable effects on the angular distribution of the emitted carbon core-hole photoelectron. These effects have already been observed experimentally using the cold target recoil ion momentum spectroscopy technique. We propose a simple classical explanation based on the intramolecular electrostatic potential to qualitatively explain the preferred directions of electron emission.

We report theoretical results of the low-energy photodetachment cross sections of the ${\mathrm{C}}_{2}\mathrm{H}{}^{\ensuremath{-}},\phantom{\rule{0.16em}{0ex}}{\mathrm{C}}_{4}\mathrm{H}{}^{\ensuremath{-}}$, and ${\mathrm{C}}_{6}\mathrm{H}{}^{\ensuremath{-}}$ hydrocarbon-chain anions. The complex Kohn variational technique is used to calculate molecular-frame transition dipole moments from the anion ground state to a photoelectron in the continuum of the neutral radical. We employ the Franck-Condon approximation and include interchannel electronic coupling to determine the low-energy photodetachment cross sections and asymmetry parameters. We discuss the behavior of the cross section, especially near thresholds, and describe the role of electronic resonances and excited channels. The theoretical results reproduce the main characteristics of recent measurements of absolute photodetachment cross sections.

Synopsis Intense, circularly polarized extreme-ultraviolet (XUV) and near-infrared (NIR) laser pulses are combined to double-ionize atomic helium via the oriented intermediate He+ (3p) resonance state. A strong and NIR-intensity dependent circular dichroism is accounted to a helicity dependent AC-Stark shift.

We present the results of attosecond angular streaking of atomic Hydrogen using elliptically polarized, 5.5 fs pulses that are centered around 770 nm, within the intensity range of 1.65 to 4 × 1014 W/cm2. We measure angular offsets in the photo-electron momentum distribution relative to the peak of the electric field of light in the polarization plane. We find a strong agreement in these results with the solutions of complete 3D-TDSE simulations. Further, we compute the contribution of coulomb effects (between the ionized electron-parent ion) to the measured angular offsets using Yukawa potential, subtracting which yields the real 'tunneling delays'.

We have developed an approach based on first principles to study the process of radiative electron attachment (REA) to linear molecules of astrophysical interest in collisions between the molecules and electrons at energies below 1 eV. The approach is based on accurate ab initio calculations of electronic bound and continuum states of the negative ion. The electronic continuum states are obtained with the complex-Kohn variational method. The benchmark calculation for the REA to the simplest negative ion CN${}^{\ensuremath{-}}$, which was recently observed in the interstellar medium, has produced a relatively low rate coefficient $\ensuremath{\alpha}(T)=7.3\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}16}$ cm${}^{3}/$s at $T=30$ K. Moreover, our results are shown to agree well with microscopic reversibility applied on a recent photodetachment experiment on CN${}^{\ensuremath{-}}$. Finally, the study confirms a previous assessment that the CN${}^{\ensuremath{-}}$ ion is unlikely be formed by REA in the interstellar medium.

We present results of a theoretical study on dissociative recombination of the HCNH+ , HCO+ and N2 H+ linear polyatomic ions at low energies using a simple theoretical model. In the present study, the indirect mechanism for recombination proceeds through the capture of the incoming electron in excited vibrational Rydberg states attached to the degenerate transverse modes of the linear ions. The strength of the non-adiabatic coupling responsible for dissociative recombination is determined directly from the near-threshold scattering matrix obtained numerically using the complex Kohn variational method. The final cross sections for the process are compared with available experimental data. It is demonstrated that at low collision energies, the major contribution to the dissociative recombination cross section is due to the indirect mechanism.

We report the results of ab initio calculations on valence photoionization of the acetylene monocation in its ground ($X$) and electronically excited ($A$) states using the complex Kohn variational method. In contrast to the $K$-shell molecular frame photoelectron angular distributions (MFPADs), which are only sensitive to the molecular geometry, these results show that the valence MFPADs are also sensitive to the electronic state of the target. Hence, the isomerization path from acetylene to vinylidene, which is mediated by a conical intersection responsible for a change in electronic state of the monocation, could, in principle, be traced through valence photoionization.

A general first-principles theory of dissociative recombination is developed for highly symmetric molecular ions and applied to ${\mathrm{H}}_{3}{\mathrm{O}}^{+}$ and ${\mathrm{CH}}_{3}^{+}$, 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.

We present a theoretical description of dissociative recombination of triatomic molecular ions having large permanent dipole moments. The study has been partly motivated by a discrepancy between experimental and theoretical cross sections for dissociative recombination of the ${\text{HCO}}^{+}$ ion. The ${\text{HCO}}^{+}$ ion has a considerable permanent dipole moment $(D\ensuremath{\approx}4\text{ }\text{D})$, which has not been taken explicitly into account in previous theoretical studies. In the present study, we include explicitly the effect of the permanent electric dipole on the dynamics of the incident electron using the generalized quantum defect theory, and we present the resulting cross section obtained. This demonstrates the possibility of applying generalized quantum defect theory to the dissociative recombination of molecular ions.