arXiv subjects

G. F. Gribakin

Publications and source records attributed to G. F. Gribakin.

At least 19 recordsLinked to original sources

arXiv2025

Dissociative positronium attachment in halogen gases

We suggest that the observed large annihilation rates of ortho-positronium ($o$-Ps) in halogen gases are due to the process of dissociative Ps attachment, ${\rm Ps} + X_2 \to {\rm Ps}X + X$, where $X$ stands for a halogen atom. This process is similar to dissociative electron attachment which leads to formation of negative ions. We calculate the cross section and rate of this process for the F$_2$ molecule, for which it is exothermic, and therefore, can occur at room temperature. We start with the Ps-F$_2$ scattering calculations which take into account electron exchange and correlations within the framework of the free-electron-gas model. The calculations reveal several resonances. Similar to the process of dissociative electron attachment, a $Σ_u$ resonance contributes to the dissociative Ps attachment at thermal energies. We determine the resonance position and width as functions of the internuclear separation, and use them as inputs for the local version of the quasiclassical theory of dissociative attachment. Our calculations yield an anomalously large rate constant for the $o$-Ps annihilation process which is only one order of magnitude lower than those observed for Br$_2$ and I$_2$.

physics.atom-ph↗

arXiv2021

B-Spline basis Hartree-Fock method for arbitrary central potentials: atoms, clusters and electron gas

An implementation of the Hartree-Fock (HF) method capable of robust convergence for well-behaved arbitrary central potentials is presented. The Hartree-Fock equations are converted to a generalized eigenvalue problem by employing a B-spline basis in a finite-size box. Convergence of the self-consistency iterations for the occupied electron orbitals is achieved by increasing the magnitude of the electron-electron Coulomb interaction gradually to its true value. For the Coulomb central potential, convergence patterns and energies are presented for a selection of atoms and negative ions, and are benchmarked against existing calculations. The present approach is also tested by calculating the ground states for an electron gas confined by a harmonic potential and also by that of uniformly charged sphere (the jellium model of alkali-metal clusters). For the harmonically confined electron-gas problem, comparisons are made with the Thomas-Fermi method and its accurate asymptotic analytical solution, with close agreement found for the electron energy and density for large electron numbers. We test the accuracy and effective completeness of the excited state manifolds by calculating the static dipole polarizabilities at the HF level and using the Random-Phase Approximation. Using the latter is crucial for the electron-gas and cluster models, where the effect of electron screening is very important. Comparisons are made for with experimental data for sodium clusters of up to $\sim $100 atoms.

physics.atom-ph↗

arXiv2021

Self annihilation of confined positronium

The effect of confinement on the self-annihilation rate of positronium is studied in three levels of approximation. Artificial restriction of the electron-positron separation leads to an increase in the annihilation rate over its vacuum value; this increase is found to diminish exponentially as the maximum separation is increased. Confinement in a hard-wall spherical cavity with the center of mass free to move throughout the cavity also increases the annihilation rate over its vacuum value; the increase depends weakly on the position of the center of mass, being larger when the center of mass is near the cavity wall. Finally, to model confinement in a pore of a microporous material, the hard wall is replaced by physically motivated electron- and positron-wall potentials; it is found that the annihilation rate is larger than its vacuum value, in contradiction to calculations of Marlotti Tanzi et al. [Phys. Rev. Lett. 116, 033401 (2016)] that assumed hard-wall confinement for the electrons, and experimental data.

physics.atom-ph↗

arXiv2021

Effect of chlorination on positron binding to hydrocarbons: experiment and theory

Measured and calculated positron binding energies are presented for a range of hydrocarbons with up to six carbon atoms (viz., methane, acetylene, ethylene, ethane, propane, butane, and hexane) and their chlorinated counterparts. Both experiment and theory confirm the large effect that the chlorine atoms have on the positron binding energy and the strong sensitivity of the binding energy to the exact position of the chlorine atoms. The experimental binding energies have been obtained by measuring positron resonant annihilation using a trap-based positron beam. The calculations are performed using the previously developed model-correlation-potential method [A. R. Swann and G. F. Gribakin, J. Chem. Phys. 149, 244305 (2018)]. The overall trends are discussed with regard to the molecular polarizability, dipole moment, and geometry. Good agreement between theory and experiment is found, with the exception of the chlorinated ethylenes and chlorinated hexane. Calculations of the electron-positron annihilation rate in the bound state are also presented.

physics.atom-ph↗

arXiv2021

Many-body theory for positronium scattering and pickoff annihilation in noble-gas atoms

The many-body-theory approach to positronium-atom interactions developed in [Phys. Rev. Lett. \textbf{120}, 183402 (2018)] is applied to the sequence of noble-gas atoms He-Xe. The Dyson equation is solved separately for an electron and positron moving in the field of the atom, with the entire system enclosed in a hard-wall spherical cavity. The two-particle Dyson equation is solved to give the energies and wave functions of the Ps eigenstates in the cavity. From these, we determine the scattering phase shifts and cross sections, and values of the pickoff annihilation parameter $^1Z_\text{eff}$ including short-range electron-positron correlations via vertex enhancement factors. Comparisons are made with available experimental data for elastic and momentum-transfer cross sections and $^1Z_\text{eff}$. Values of $^1Z_\text{eff}$ for He and Ne, previously reported in [Phys. Rev. Lett. \textbf{120}, 183402 (2018)], are found to be in near-perfect agreement with experiment, and for Ar, Kr, and Xe within a factor of 1.2.

physics.atom-ph↗

arXiv2020

Effect of molecular constitution and conformation on positron binding and annihilation in alkanes

The model-potential approach previously developed by the authors to study positron interactions with molecules is used to calculate the positron binding energy for $n$-alkanes (C$_n$H$_{2n+2}$) and the corresponding cycloalkanes (C$_n$H$_{2n}$). For $n$-alkanes, the dependence of the binding energy on the conformation of the molecule is investigated, with more compact structures showing greater binding energies. As a result, thermally averaged binding energies for larger alkanes ($n\gtrsim 9$) show a strong temperature dependence in the range of 100-600 K. This suggests that positron resonant annihilation can be used as a probe of rotational (trans-gauche) isomerization of $n$-alkanes. In particular, the presence of different conformers leads to shifts and broadening of vibrational Feshbach resonances in the annihilation rate, as observed with a trap-based low-energy positron beam.

physics.atom-ph↗

arXiv2020

Model-potential calculations of positron binding, scattering, and annihilation for atoms and small molecules, using a Gaussian basis

A model-potential method is employed to calculate binding, elastic scattering, and annihilation of positrons for a number of atoms and small nonpolar molecules, namely, Be, Mg, He, Ar, H$_2$, N$_2$, Cl$_2$, and CH$_4$. The model potential contains one free parameter for each type of atom within the target. Its values are chosen to reproduce existing ab initio positron-atom binding energies or scattering phase shifts. The calculations are performed using a Gaussian basis for the positron states, and we show how to obtain values of the scattering phase shifts and normalized annihilation rate $Z_{\rm eff}$ from discrete positive-energy pseudostates. Good agreement between the present results and existing calculations and experimental data, where available, is obtained, including the $Z_{\rm eff}$ value for CH$_4$, which is strongly enhanced by a low-lying virtual positron state. An exception is the room-temperature value of $Z_{\rm eff}$ for Cl$_2$, for which the present value is much smaller than the experimental value obtained over 50 years ago. Our calculations predict that among the molecular targets studied, only Cl$_2$ might support a bound state for the positron, with a binding energy of a few meV.

physics.atom-ph↗

arXiv2019

Positron Binding and Annihilation in Alkane Molecules

A model-potential approach has been developed to study positron interactions with molecules. Binding energies and annihilation rates are calculated for positron bound states with a range of alkane molecules, including rings and isomers. The calculated binding energies are in good agreement with experimental data, and the existence of a second bound state for $n$-alkanes (C$_n$H$_{2n+2}$) with $n\geq12$ is predicted in accord with experiment. The annihilation rate for the ground positron bound state scales linearly with the square root of the binding energy.

physics.atom-ph↗

arXiv2018

Calculations of positron binding and annihilation in polyatomic molecules

A model-potential approach to calculating positron-molecule binding energies and annihilation rates is developed. Unlike existing ab initio calculations, which have mostly been applied to strongly polar molecules, the present methodology can be applied to both strongly polar and weakly polar or nonpolar systems. The electrostatic potential of the molecule is calculated at the Hartree-Fock level, and a model potential that describes short-range correlations and long-range polarization of the electron cloud by the positron is then added. The Schrodinger equation for a positron moving in this effective potential is solved to obtain the binding energy. The model potential contains a single adjustable parameter for each type of atom present in the molecule. The wave function of the positron bound state may be used to compute the rate of electron-positron annihilation from the bound state. As a first application, we investigate positron binding and annihilation for the hydrogen cyanide (HCN) molecule. Results for the binding energy are found to be in accord with existing calculations, and we predict the rate of annihilation from the bound state to be $Γ=0.1$--$0.2 \times 10^9~\text{s}^{-1}$.

physics.atom-ph↗

arXiv2018

Density-matrix description of partially coherent spin-orbit wave packets produced in short-laser-pulse photodetachment

We investigate orbital alignment dynamics within the valence shell of atoms in coherently excited $j=3/2,1/2$ fine-structure manifolds generated by short-pulse photodetachment of F$^-$, Cl$^-$ and Br$^-$ anions. Using Keldysh-type theory, we calculate the density matrix of the residual atoms generated by few-cycle pulses, whose elements determine the populations and coherence among the electronic states. Our calculations demonstrate that the degree of atomic coherence can be represented by a near universal function of the ratio between the pulse duration $\tildeτ_p$ and the beat period $τ_{j'j}$ of the atomic system, which allows one to characterize the coherence generated in atomic states.

quant-ph↗

arXiv2018

Many-body theory for positronium-atom interactions

A many-body-theory approach has been developed to study positronium-atom interactions. As first applications, we calculate the elastic scattering and momentum-transfer cross sections and the pickoff annihilation rate $^1Z_\text{eff}$ for Ps collisions with He and Ne. The cross section for He is in agreement with previous coupled-state calculations, and the momentum-transfer cross section for Ne agrees with available experimental data. $^1Z_\text{eff}$ is found to be 0.13 and 0.26 for He and Ne, respectively, in excellent agreement with the measured values.

physics.atom-ph↗

arXiv2017

Calculations of positronium-atom scattering using a spherical cavity

Positronium (Ps) scattering by noble-gas atoms (He, Ne, Ar, Kr, and Xe) is studied in the frozen-target approximation and with inclusion of the van der Waals interaction. Single-particle electron and positron states in the field of the target atom are calculated, with the system enclosed by a hard spherical wall. The two-particle Ps wave function is expanded in these states, and the Hamiltonian matrix is diagonalized, giving the Ps energy levels in the cavity. Scattering phase shifts, scattering lengths, and cross sections are extracted from these energies and compared with existing calculations and experimental data. Analysis of the effect of the van der Waals interaction shows that it cannot explain the recent experimental data of Brawley et al. for Ar and Xe [Phys. Rev. Lett. 115, 223201 (2015)].

physics.atom-ph↗

arXiv2017

Mode coupling and multiquantum vibrational excitations in Feshbach-resonant positron annihilation in molecules

The dominant mechanism of low-energy positron annihilation in polyatomic molecules is through positron capture in vibrational Feshbach resonances (VFR). In this paper we investigate theoretically the effect of anharmonic terms in the vibrational Hamiltonian on the positron annihilation rates. Such interactions enable positron capture in VFRs associated with multiquantum vibrational excitations, leading to enhanced annihilation. Mode coupling can also lead to faster depopulation of VFRs, thereby reducing their contribution to the annihlation rates. To analyze this complex picture, we use coupled-cluster methods to calculate the anharmonic vibrational spectra and dipole transition amplitudes for chloroform, chloroform-$d_1$, 1,1-dichloroethylene, and methanol, and use these data to compute positron resonant annihilation rates for these molecules. Theoretical predictions are compared with the annihilation rates measured as a function of incident positron energy. The results demonstrate the importance of mode coupling in both enhancement and suppression of the VFR. There is also experimental evidence for the direct excitation of multimode VFR. Their contribution is analyzed using a statistical approach, with an outlook towards more accurate treatment of this phenomenon.

physics.atom-ph↗

arXiv2017

Vibrational Feshbach Resonances Mediated by Nondipole Positron-Molecule Interactions

Measurements of energy-resolved positron-molecule annihilation show the existence of positron binding and vibrational Feshbach resonances. The existing theory describes this phenomenon successfully for the case of infrared-active vibrational modes which allow dipole coupling between the incident positron and the vibrational motion. Presented here are measurements of positron-molecule annihilation made using a recently developed cryogenic positron beam capable of significantly improved energy resolution. The results provide evidence of resonances associated with infrared-inactive vibrational modes, indicating that positron-molecule bound states may be populated by nondipole interactions. The anticipated ingredients for a theoretical description of such interactions are discussed.

physics.atom-ph↗

arXiv2017

Enhancement factors for positron annihilation on valence and core orbitals of noble-gas atoms

Annihilation momentum densities and correlation enhancement factors for low-energy positron annihilation on valence and core electrons of noble-gas atoms are calculated using many-body theory. s, p and d-wave positrons of momenta up to the positronium-formation threshold of the atom are considered. The enhancement factors parametrize the effects of short-range electron-positron correlations which increase the annihilation probability beyond the independent-particle approximation. For all positron partial waves and electron subshells, the enhancement factors are found to be relatively insensitive to the positron momentum. The enhancement factors for the core electron orbitals are also independent of the positron angular momentum. The largest enhancement factor ($\sim 15$) is found for the 5p orbital in Xe, while the values for the core orbitals are typically $\sim 1.5$.

physics.atom-ph↗

arXiv2017

Effective radius of ground- and excited-state positronium in collisions with hard walls

We determine effective collisional radii of positronium (Ps) by considering Ps states in hard-wall spherical cavities. $B$-spline basis sets of electron and positron states inside the cavity are used to construct the states of Ps. Accurate Ps energy eigenvalues are obtained by extrapolation with respect to the numbers of partial waves and radial states included in the bases. Comparison of the extrapolated energies with those of a pointlike particle provides values of the effective radius $ρ_{nl}$ of Ps($nl$) in collisions with a hard wall. We show that for $1s$, $2s$, and $2p$ states of Ps, the effective radius decreases with the increasing Ps center-of-mass momentum, and find $ρ_{1s}=1.65$ a.u., $ρ_{2s}=7.00$ a.u., and $ρ_{2p}=5.35$ a.u. in the zero-momentum limit.

physics.atom-ph↗

arXiv2017

Comment on "Gamma-ray spectra from low-energy positron annihilation processes in molecules"

In the article by Ma~\emph{et al.}~[Phys.~Rev.~A {\bf 94}, 052709 (2016)], $γ$-ray spectra for positron annihilation on molecules were calculated in the independent-particle approximation with the positron wavefunction set to unity. Based on comparisons with experimental data they concluded that inner valence electrons play a dominant role in positron annihilation. These conclusions are incorrect and resulted from fallacious analysis that ignored the known effect of the positron wavefunction on the spectra.

physics.atom-ph↗

arXiv2016

Comment on "Direct photodetachment of F$^-$ by mid-infrared few-cycle femtosecond laser pulses"

Multiphoton detachment of F$^-$ by strong few-cycle laser pulses was studied by Shearer and Monteith using a Keldysh-type approach [Phys. Rev. A 88, 033415 (2013)]. We believe that this work contained errors in the calculation of the detachment amplitude and photoelectron spectra. We describe the necessary corrections to the theory and show that the results, in particular, the interference features of the photoelectron spectra, appear noticeably different.

physics.atom-ph↗