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 $Γ=0.1$--$0.2 \times 10^9~\text{s}^{-1}$.
A long-standing problem to account for the electron-positron annihilation in positron Hydrogen scattering above the Positronium formation threshold has been resolved by the use of the three-body Faddeev formalism. The multichannel three-body theory for scattering states in presence of a complex absorbing potential is developed in order to compute the direct $e^+ e^-$ annihilation amplitude, the amplitude of Positronium formation and respective cross sections. A number of $e^+ e^-$ direct annihilation cross sections and Positronium formation cross sections in the energy gap between Ps$(1s)$ and…
The aim of this work is to identify the mechanisms responsible for very large rates and other peculiarities observed in low-energy positron annihilation on molecules. The two mechanisms considered are: (i) Direct annihilation of the incoming positron with one of the molecular electrons. This mechanism dominates for atoms and small molecules. I show that its contribution to the annihilation rate can be related to the positron elastic scattering cross section. This mechanism is characterized by strong energy dependence of the annihilation rate at small positron energies if a low-lying virtual le…
Enhanced positron annihilation on polyatomic molecules is a long-standing and complex problem. We report the results of calculations of resonant positron annihilation on methyl halides. A free parameter of our theory is the positron binding energy. A comparison with energy-resolved annihilation rates measured for CH$_3$F, CH$_3$Cl, CH$_3$Br [Barnes et al. Phys. Rev. A {\bf 74}, 012706 (2006)] shows good agreement and yields estimates of the binding energies.
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 insensiti…
Diagrammatic many-body theory is used to calculate the scattering phase shifts, normalized annihilation rates $Z_{\rm eff}$ and annihilation gamma spectra for positron collisions with the hydrogen-like ions He$^+$, Li$^{2+}$, B$^{4+}$ and F$^{8+}$. Short-range electron-positron correlations and longer-range positron-ion correlations are accounted for by evaluating nonlocal corrections to the annihilation vertex and the exact positron self-energy. The numerical calculation of the many-body theory diagrams is performed using B-spline basis sets. To elucidate the rôle of the positron-ion repulsio…
This article presents an overview of current understanding of the interaction of low-energy positrons with molecules with emphasis on resonances, positron attachment and annihilation. Annihilation rates measured as a function of positron energy reveal the presence of vibrational Feshbach resonances (VFR) for many polyatomic molecules. These resonances lead to strong enhancement of the annihilation rates. They also provide evidence that positrons bind to many molecular species. A quantitative theory of VFR-mediated attachment to small molecules is presented. It is tested successfully for select…
Positron scattering and annihilation on noble gas atoms below the positronium formation threshold is studied ab initio using many-body theory methods. The many-body theory provides a near-complete understanding of the positron-noble-gas-atom system at these energies and yields accurate numerical results. It accounts for positron-atom and electron-positron correlations, e.g., polarization of the atom by the incident positron and the non-perturbative process of virtual positronium formation. These correlations have a large effect on the scattering dynamics and result in a strong enhancement of t…
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.
A method is proposed for detecting positron-atom bound states by observing enhanced positron annihilation due to electronic Feshbach resonances at electron-volt energies. The method is applicable to a range of open-shell transition metal atoms which are likely to bind the positron: Fe, Co, Ni, Tc, Ru, Rh, Sn, Sb, Ta, W, Os, Ir, and Pt. Estimates of their binding energies are provided.
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 couple…
Positrons bind to molecules leading to vibrational excitation and spectacularly enhanced annihilation. Whilst positron binding energies have been measured via resonant annihilation spectra for $\sim$90 molecules in the past two decades, an accurate \emph{ab initio} theoretical description has remained elusive. Of the molecules studied experimentally, calculations exist for only 6, and for these, standard quantum chemistry approaches have proved severely deficient, agreeing with experiment to at best 25% accuracy for polar molecules, and failing to predict binding in nonpolar molecules. The mec…
The process of a positron $\unicode{x2013}$ bound-electron annihilation with simultaneous emission of two photons is investigated theoretically. A fully relativistic formalism based on $\textit{ab initio}$ QED description of the process is worked out. The developed approach is applied to evaluate the annihilation of a positron with $K$-shell electrons of a silver atom, for which a strong contradiction between theory and experiment was previously stated. The results obtained here resolve this long-standing disagreement and, moreover, demonstrate a sizeable difference with approaches so far used…
Calculations of gamma spectra for positron annihilation on a selection of molecules, including methane and its fluoro-substitutes, ethane, propane, butane and benzene are presented. The annihilation gamma spectra characterise the momentum distribution of the electron-positron pair at the instant of annihilation. The contribution to the gamma spectra from individual molecular orbitals is obtained from electron momentum densities calculated using modern computational quantum chemistry density functional theory tools. The calculation, in its simplest form, effectively treats the low-energy (therm…
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 …
In this paper we use a zero-range potential (ZRP) method to model positron interaction with molecules. This allows us to investigate the effect of molecular vibrations on positron-molecule annihilation using the van der Waals dimer Kr2 as an example. We also use the ZRP to explore positron binding to polyatomics and examine the dependence of the binding energy on the size of the molecule for alkanes. We find that a second bound state appears for a molecule with ten carbons, similar to recent experimental evidence for such a state emerging in alkanes with twelve carbons.
$γ$-ray spectra for positron annihilation with the core and valence electrons of the noble gas atoms Ar, Kr and Xe is calculated within the framework of diagrammatic many-body theory. The effect of positron-atom and short-range positron-electron correlations on the annihilation process is examined in detail. Short-range correlations, which are described through non-local corrections to the vertex of the annihilation amplitude, are found to significantly enhance the spectra for annihilation on the core orbitals. For Ar, Kr and Xe, the core contributions to the annihilation rate are found to be …
Bound state properties of the negatively charged Ps$^{-}$ ion (or $e^{-} e^{+} e^{-}$) are discussed. The expectation values of operators which correspond to these properties have been determined with the use of the highly accurate wave functions constructed for this ion. Our best variational energy obtained for the Ps$^{-}$ ion is $E$ = -0.2620050 7023298 0107770 40051 $a.u.$ Annihilation of the electron-positron pair(s) in the negatively charged Ps$^{-}$ ion (or $e^{-} e^{+} e^{-}$) is considered in detail. By using accurate values for a number annihilation rates $Γ_{n γ}$, where $n$ = 1, 2,…
A new {\it ab initio} theoretical formulation to calculate $Z_{eff}$ and hence the positron annihilation rates is presented using the on-shell and half-offshell T-matrix scattering amplitudes without any explicit use of the scattering wave function. The formulation is exact and universal, as long as the dynamics of the system can be described by a Lippmann-Schwinger type equation. It could serve as an effective tool as all the $T-$, $K-$, and $S-$matrix formulations, yield directly the scattering amplitudes; not the wave function. We also present a basic numerical test of the formulation.
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.
$γ$ spectra for positron annihilation in noble-gas atoms are calculated using many-body theory for positron momenta up to the positronium-formation threshold. This data is used, together with time-evolving positron-momentum distributions determined in [arXiv:1706.01434 (2017)], to calculate the time-varying $γ$ spectra produced during positron cooling in noble gases. The $γ$-spectra and their $\bar{S}$ and $\bar{W}$ shape parameters are shown to be sensitive probes of the time evolution of the positron momentum distribution, and thus provide a means of studying positron cooling that is complem…
A small difference between the energy of the para-positronium (p-Ps) and ortho-positronium (o-Ps) states suggests the possibility of superposition of p-Ps and o-Ps during the formation of positronium (Ps) from pre-Ps terminating its migration in the matter in a void ('free volume'). It is shown that such a superposition decohere in the basis of p-Ps and o-Ps and the decoherence time is estimated. The time scale of the decoherence estimated here motivates respective correction in decomposition of the positron annihilation lifetime spectra. The way of the correction is sketched. The timescale of…
A many-body theory approach to the calculation of gamma spectra of positron annihilation on many-electron atoms is developed. We evaluate the first-order correlation correction to the annihilation vertex and perform numerical calculations for the noble gas atoms. Extrapolation with respect to the maximal orbital momentum of the intermediate electron and positron states is used to achieve convergence. The inclusion of correlation corrections improves agreement with experimental gamma spectra.
A problem to account for the direct electron-positron annihilation in positron-hydrogen scattering above the positronium formation threshold has been resolved within the time independent formalism. The generalization of the optical theorem is derived for the case when an absorption potential is present in the Hamiltonian. With this theorem the annihilation cross section is fully determined by scattering amplitudes. This allows us to separate out analytically the contribution of the positronium formation from the overall annihilation cross section. The rest is determined as the direct annihilat…
The annihilation parameters of positrons with electrons in different shells of Argon, Iron and Copper atoms are calculated below the positronium (Ps) formation thresholds. Quite accurate ab initio calculations of the bound state wavefunctions of Argon, Iron and Copper orbitals are obtained from Cowan computer code. A least-squares variational method (LSVM) is used for determining the wavefunction of the positrons. The program is employed for calculating the s-wave partial cross sections of positrons scattered by Iron and Copper atoms. Our results of the effective charge are compared with avail…
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 …
Many-body theory is developed to calculate the $γ$-spectra for positron annihilation with valence and core electrons in the noble gas atoms. A proper inclusion of correlation effects and core annihilation provides for an accurate description of the measured spectra [Iwata \textit{et al.}, Phys. Rev. Lett. {\bf 79}, 39 (1997)]. The theory enables us to calculate the enhancement factors $γ_{nl}$, which describe the effect of electron-positron correlations for annihilation on individual electron orbitals $nl$. We find that the enhancement factors scale with the orbital ionization energy $I_{nl}$ …
The single photon annihilation contributions for the positronium ground state hyperfine splitting are calculated analytically to order $m_eα^6$ using NRQED. Based on intuitive physical arguments the same result can also be determined by a trivial calculation using results from existing literature. Our result completes the hyperfine splitting calculation to order $m_eα^6$. We compare the theoretical prediction with the most recent experimental measurement.
Understanding the dynamics of positron cooling in gases, including the fraction of positrons surviving to thermalisation, is critical for accurate interpretation of positron lifetime spectra, for the development of efficient positron cooling in traps and accumulators, and for a cryogenically cooled, ultra-high-energy-resolution, trap-based positron beam. Here, positron cooling and annihilation in noble gases is simulated using accurate scattering and annihilation cross sections calculated \emph{ab initio} with many-body theory. It is shown that a strikingly small fraction of positrons survive …
A large number of bound state properties of the four-body muonium-positronium system MuPs (or $μ^{+} e^{-}_2 e^{+}$) are determined to high accuracy. Based on these expectation values we predict that the weakly-bound four-body MuPs system has the `two-body' cluster structure Mu + Ps. The two neutral clusters Mu ($μ^{+} e^{-}$) and Ps ($e^{+} e^{-}$) interact with each other by the attractive van der Waals forces. By using our expectation values of the electron-positron delta-functions we evaluated the half-life $τ_a$ of the MuPs system against annihilation of the electron-positron pair: $τ_a =…
The two-photon annihilation of a positron with an electron bound in the 1s state of a H-like ion is calculated within the fully relativistic QED framework. The interaction with the nucleus is treated nonperturbatively, thus allowing the calculations to be carried out for the annihilation with strongly-bound inner shells of heavy ions. Infrared divergences, appearing when one of the emitted photons approaches the low-frequency limit, are accurately eliminated from final expressions. The total cross section of the two-photon and one-photon annihilation processes are compared for a wide range of …
The confined variational method is used to generate a basis of correlated gaussians to describe the interaction region wave function for positron scattering from the H$_2$ molecule. The scattering length was $\approx -2.7$ $a_0$ while the zero energy $Z_{\rm eff}$ of 15.7 is compatible with experimental values. The variation of the scattering length and $Z_{\rm eff}$ with inter-nuclear distance was surprisingly rapid due to virtual state formation at $R \approx 3.4$ $a_0$.
In the annihilation of a positron with a bound atomic electron, the virtual gamma photon created may excite the atomic nucleus. We put forward this effect as a spectroscopic tool for an energy-selective excitation of nuclear transitions. This scheme can efficiently populate nuclear levels of arbitrary multipolarities in the MeV regime, including monopole transitions and giant resonances. In certain cases, it may have a higher cross sections than the conventionally used Coulomb excitation.
The life-time of the four-body atomic system MuPs ($μ^{+} e^{-}_2 e^{+}$ or muonium-positronium) against positron annihilation has been evaluated as $τ= \frac{1}Γ \approx 4.076453 \cdot 10^{-10}$ $sec$. Various annihilation rates for MuPs are determined to a good numerical accuracy, e.g., $Γ_{2 γ} \approx$ 2.446485$\cdot 10^{9}$ $sec^{-1}$, $Γ_{3 γ} \approx$ 6.62798$\cdot 10^{6}$ $sec^{-1}$, $Γ_{4 γ} \approx$ 3.61680$\cdot 10^{3}$ $sec^{-1}$, $Γ_{5 γ} \approx$ 6.32973 $sec^{-1}$. The hyperfine structure splitting for the ground state in the MuPs system has also been evaluated as $Δ$ = 23.078 $…
It is known for a long time that the long range asymptotic behavior of the Hartree-Fock orbitals is different from that of the orbitals in the local potential. However, there is no consensus about observable physical effects associated with this asymptotics. Here we argue that weaker decrease of the Hartree-Fock orbitals at large distances is responsible for the positron annihilation on the inner shell electrons, which is observed experimentally.
The rate for complete two-photon annihilation of molecular positronium Ps$_{2}$ is reported. This decay channel involves a four-body collision among the fermions forming Ps$_{2}$, and two photons of 1.022 MeV, each, as the final state. The quantum electrodynamics result for the rate of this process is found to be $Γ_{Ps_{2} \rightarrow γγ}$ = 9.0 $\times 10^{-12}$ s$^{-1}$. This decay channel completes the most comprehensive decay chart for Ps$_{2}$ up to date.
Bound state properties and positron annihilation in the negatively charged Ps$^{-}$ ion. On thermal sources of fast positrons and annihilation $γ$-quanta in our Galaxy
Bound electron contribution to the Doppler-shift of gamma-ray spectra in the positron-electron annihilation process of molecular methane has been studied in gas phase. Two accurate ab initio quantum mechanical schemes, i.e. the delocalized molecular orbital (MO) and the localized natural bond orbital (NBO) schemes, are applied to study the multi-centred methane molecule. The present ab initio calculations of methane indicate that the C-H bonds are polarized with the partial negative charge of -0.36 a.u. on the carbon atom and the partial positive charge of +0.09 a.u. on each of the hydrogen at…
