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Roman Čurík

Publications and source records attributed to Roman Čurík.

13 recordsLinked to original sources

Connecting Collisional and Photofragmentation Resonances in the H$_2$ Ungerade Symmetry

A recently developed energy-dependent frame transformation theory that incorporates both ionization and dissociation channels of the H$_2$ molecule, is extended to treat the ungerade states that occur both in dissociative recombination and as the final state in ground state photoabsorption. The theoretical treatment includes the rotational degrees of freedom and is benchmarked against a two-dimensional model that can be solved with high accuracy and also compared with photoabsorption experiments. Analysis of the resulting spectra shows how the same resonances appear in very different observables, often with quite different line shapes.

physics.chem-ph↗

Chemistry and ro-vibrational excitation of HeH$^+$ in the Planetary Nebula NGC 7027

HeH$^+$ belongs to the class of "reactive" ions that can be destroyed so quickly that chemical formation and destruction rates may compete with inelastic rates and should be considered when solving the statistical equilibrium equations. This so-called chemical "pumping" or "excitation" effect is investigated here for the first time in HeH$^+$. The chemical evolution of HeH$^+$ in NGC 7027 is modeled with the CLOUDY photoionization code using updated reaction rate coefficients. The non-LTE analysis of the three observed HeH$^+$ emission lines is then performed with the CLOUDY and RADEX codes using an extensive set of spectroscopic and inelastic collisional data suitable for the specific high-temperature environment of NGC 7027. In a second approach, chemical formation and destruction rates of HeH$^+$ are implemented in RADEX. This code is combined with MCMC sampling (performed on the RADEX-parameters space) to extract the best-fit HeH$^+$ column density and physical conditions from the observed line fluxes. The CLOUDY and RADEX non-LTE results are found to be in good agreement, and the $\upsilon=1-0 \ P(2)/P(1)$ line ratio is better than 20%. Agreement to better than a factor of 2.3 is obtained when including the reaction between He($2^3S$) and H as an additional source of HeH$^+$. The RADEX/MCMC model with chemical pumping is found to reproduce both the observed line fluxes and the line ratio to 20%. Our results suggest that additional HeH$^+$ lines must be detected in NGC 7027 to better constrain the physical conditions via non-LTE models. Uncertainties in collisional (reactive and inelastic) data of HeH$^+$ have been largely reduced in this work. The three observed lines are not sensitive to chemical pumping while excited "short-lived" levels are significantly overpopulated with respect to a non-LTE model neglecting chemical excitation.

astro-ph.GA↗

Unimolecular processes in diatomic carbon anions at high rotational excitation

On the millisecond to second time scale, stored beams of diatomic carbon anions C$_2{}^-$ from a sputter ion source feature unimolecular decay of yet unexplained origin by electron emission and fragmentation. To account for the magnitude and time dependence of the experimental rates, levels with high rotational and vibrational excitation are modeled for the lowest electronic states of C$_2{}^-$, also including the lowest quartet potential. Energies, spontaneous radiative decay rates (including spin-forbidden quartet-level decay), and tunneling dissociation rates are determined for a large number of highly excited C$_2{}^-$ levels and their population in sputter-type ion sources is considered. For the quartet levels, the stability against autodetachment is addressed and recently calculated rates of rotationally assisted autodetachment are applied. Non-adiabatic vibrational autodetachment rates of high vibrational levels in the doublet C$_2{}^-$ ground potential are also calculated. The results are combined to model the experimental unimolecular decay signals. Comparison of the modeled to the experimental rates measured at the Croygenic Storage Ring (CSR) gives strong evidence that C$_2{}^-$ ions in quasi-stable levels of the quartet electronic states are the so far unidentified source of unimolecular decay.

physics.chem-ph↗

Autodetachment of diatomic carbon anions from long-lived high-rotation quartet states

Highly excited C$_2{}^{-}$ ions prominently feature electron detachment at a mean decay time near 3 milliseconds with hitherto unexplained origin. Considering various sources of unimolecular decay, we attribute the signal to the electronic C$^4Σ^+_u$ state. Quartet C$_2{}^{-}$ levels are found to be stabilized against autodetachment by high rotation. Time constants of their rotationally assisted autodetachment into levels opening energetically at lower rotation are calculated by a theory based on the non-local resonance model. For some final levels of significantly less rotation the results conclusively explain the puzzling observations.

physics.chem-ph↗

Competing Ionization and Dissociation in the H$_2$ Gerade System

A numerically solvable two-dimensional (2D) model, employed by the authors to study the dissociative recombination of H$_2^+$ in the ungerade symmetry [Phys. Rev. A $\mathbf{98}$, 062706 (2018)], is extended to describe the collision process in the gerade symmetry of H$_2$. In this symmetry the ionization and dissociation processes are driven primarily by the direct, curve-crossing mechanism. The model is represented by a set of three coupled electronic channels in 2D, in the space of $s,p,d$ partial waves of the colliding electron. We demonstrate that the Born-Oppenheimer properties of the H$_2$ molecule in the relevant range of internuclear distances can be described by such a model. The molecular rotational degrees of freedom are accounted for by the rotational frame transformation. The numerical solution of the model is discussed and the resulting rovibrationally inelastic and dissociative recombination cross sections are compared with the available data.

physics.chem-ph↗

Energy-dependent frame transformation theory for dissociative recombination

The energy-dependent frame transformation theory of Gao and Greene 1990 [Phys. Rev. A {\bf 42}, 6946 (1990)] is extended to yield quantitatively accurate description of the dissociative recombination process. Evidence is presented to show that direct application of the original theory leads to inaccurate cross sections. A major revision, based on an interaction-free back-propagation of the Born-Oppenheimer solutions, markedly improves the frame transformation theory, reducing its average error by orders of magnitude. The original theory and its extension are tested on the previously explored 2D model that is tailored to describe the singlet ungerade states of molecular hydrogen. The 2D model can be solved exactly (within the numerical accuracy) without implementing the Born-Oppenheimer approximation. These exact results then serve as a benchmark for the frame transformation theory developed in this paper.

physics.chem-ph↗

Dissociative recombination of cold HeH$^+$ ions

The HeH$^+$ cation is the simplest molecular prototype of the indirect dissociative recombination (DR) process that proceeds through electron capture into Rydberg states of the corresponding neutral molecule. This Letter develops the first application of our recently developed energy-dependent frame transformation theory to the indirect DR processes. The theoretical model is based on the multichannel quantum-defect theory with the vibrational basis states computed using exterior complex scaling (ECS) of the nuclear Hamiltonian. The ab initio electronic R-matrix theory is adopted to compute quantum defects as functions of the collision energy and of the internuclear distance. The resulting DR rates are convolved over the beam energy distributions relevant to a recent experiment at the Cryogenic Storage Ring, giving good agreement between the experiment and the theory.

physics.chem-ph↗

On the validity of the Born-Oppenheimer approximation in the indirect dissociative recombination process

An alternative method is introduced to solve a simple two-dimensional models describing vibrational excitation and dissociation processes during the electron-molecule collisions. The model works with one electronic and one nuclear degree of freedom. The two-dimensional $R$-matrix can be constructed simultaneously on the electronic and nuclear surfaces using all three forms developed previously for electron-atom and electron-molecule collisions. These are the eigenchannel $R$-matrix form, inversion technique of Nesbet and Robicheaux, and the Wigner-Eisenbud-type form using expansion over the poles of the symmetrized Hamiltonian. The 2D $R$-matrix method is employed to solve a simple model tailored to describe the dissociative recombination and the vibrational excitation of H$_2^+$ cation in the singlet ungerade symmetry $^1Σ_u$. These results then serve as a (near-exact) benchmark for the following calculation in which the $R$-matrix states are replaced by their Born-Oppenheimer approximations. The accuracy of this approach and its correction with the first-order nonadiabatic couplings are discussed.

physics.chem-ph↗

$R$-matrix calculations of electron collisions with lithium atom at low energies

$R$-matrix calculations of the electron collisions with lithium atom at energies below the $3s$ excitation threshold are presented. The $^1S^e$, $^3S^e$ and $^1P^o$ phase shifts calculated in the near-threshold energy range are in excellent agreement with previous theoretical studies. The threshold behavior of the $^3P^o$ phase shift is accurately analyzed along with the resonance located at the scattering energy $\sim60$ meV. The phase shifts and cross sections calculated here show two resonances below the $3s$ threshold that have not been previously reported.

physics.atom-ph↗

Shape resonances of Be$^-$ and Mg$^-$ investigated with method of analytic continuation

The regularized method of analytic continuation is used to study the low-energy negative ion states of beryllium (configuration 2$s^2\varepsilon p\; ^2P$) and magnesium (configuration 3$s^2\varepsilon p\; ^2P$) atoms. The method applies an additional perturbation potential and it requires only routine bound-state multi-electron quantum calculations. Such computations are accessible by most of the free or commercial quantum chemistry software available for atoms and molecules. The perturbation potential is implemented as a spherical Gaussian function with a fixed width. Stability of the analytic continuation technique with respect to the width and with respect to the input range of electron affinities is studied in detail. The computed resonance parameters $E_r$=0.282 eV, $Γ$=0.316 eV for the $2p$ state of Be$^-$ and $E_r$=0.188 eV, $Γ$=0.167 for the $3p$ state of Mg$^-$, agree well with the best results obtained by much more elaborated and computationally demanding present-day methods.

physics.chem-ph↗

Dissociative recombination by frame transformation to Siegert pseudostates: A~comparison with a numerically solvable model

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 dissociative recombination for real molecular targets. The second, approximate, set of calculations employs a combination of multi-channel quantum defect theory and frame transformation into a basis of Siegert pseudostates. The cross sections computed with the two methods are compared in detail for collision energies from 0 to 2 eV.

physics.atom-ph↗

Inelastic low-energy collisions of electrons with HeH$^+$: rovibrational excitation and dissociative recombination

Inelastic low-energy (0--1 eV) collisions of electrons with HeH$^+$ cations are treated theoretically, with a focus on the rovibrational excitation and dissociative recombination (DR) channels. In an application of {\it ab initio} multichannel quantum defect theory (MQDT), the description of both processes is based on the Born-Oppenheimer quantum defects. The quantum defects were determined using the R-matrix approach in two different frames of reference: the center-of-charge and the center-of-mass frames. The results obtained in the two reference systems, after implementing the Fano-Jungen style rovibrational frame-transformation technique, shows differences in the rate of convergence for these two different frames of reference. We find good agreement with the available theoretically predicted rotationally inelastic thermal rate coefficients. Our computed DR rate also agrees well with available experimental results. Moreover, several computational experiments shed light on the role of rotational and vibrational excitations in the indirect DR mechanism that governs the low energy HeH$^+$ dissociation process. While the rotational excitation is several orders of magnitude more probable process at the studied collision energies, the closed-channel resonances described by the high-n, rotationally excited neutral molecules of HeH contribute very little to the dissociation probability. But the situation is very different for resonances defined by the high-n, vibrationally excited HeH molecules, which are found to dissociate with approximately 90% probability.

physics.chem-ph↗

Adiabatic potential energy curves of long-range Rydberg molecules: Two-electron R-matrix approach

We introduce a computational method developed for study of long-range molecular Rydberg states of such systems that can be approximated by two electrons in a model potential of the atomic cores. Only diatomic molecules are considered. The method is based on a two-electron \rmath approach inside a sphere centered on one of the atoms. The wave function is then connected to a Coulomb region outside the sphere via multichannel version of the Coulomb Green's function. This approach is put into a test by its application to a study of Rydberg states of the hydrogen molecule for internuclear distances $R$ from 20 to 400 bohrs and energies corresponding to $n$ from 3 to 22. The results are compared with previous quantum chemical calculations (lower quantum numbers $n$) and computations based on contact potential models (higher quantum numbers $n$).

physics.chem-ph↗