arXiv subjects

D. G. Green

Publications and source records attributed to D. G. Green.

At least 19 recordsLinked to original sources

arXiv2026

Diagrammatic Monte Carlo for positron-molecule many-body theory

A diagrammatic Monte Carlo evaluation of the ladder series contributions to the correlation potential (self energy) of a positron in the field of a molecule is presented. The $GW$@TDHF, virtual-positronium ($T$-matrix), and positron-hole Goldstone ladder series contributions are stochastically sampled order-by-order within the Tamm-Dancoff approximation, which is exact for the latter two classes, with Ces{á}ro-Riesz resummation used to extrapolate to infinite order. Gaussian bases are employed and Coulomb matrix elements are represented via density fitting, with the three centre integrals the largest arrays required to be stored in memory. The stochastic approach thus realizes a reduction in memory of the largest arrays required on the order of the number of molecular orbitals in the basis $N\sim$10$^2$--10$^3$ compared to the exact deterministic solution of Bethe-Salpeter equations [J. Hofierka, B. Cunningham, C. M. Rawlins, C. H. Patterson and D. G. Green, Nature {\bf 606}, {688} (2022)]. Benchmark results for lithium hydride show quantitative agreement with exact diagonalisation, notably demonstrating the successful stochastic summation of the virtual-positronium infinite electron-positron ladder series.

physics.chem-ph↗

arXiv2026

Many-body theory predictions of positron binding energies in five-membered heterocycles involving N, O, S and NH substituents

Positron binding energies and Dyson orbitals for five-membered heterocycles with N, O, S and NH substituents are predicted \emph{ab initio} via many-body theory. The positron-molecule correlation potential (self energy) is calculated via solution of Bethe-Salpeter equations that describe the positron-induced polarization of the target and screening of the electron-positron Coulomb interaction at the $GW$@BSE level, the infinite electron-positron ladder series that describes the crucially important process of virtual positronium formation, and the analogous positron-hole ladder series. The all-order calculations employ Gaussian-orbital bases and are implemented in the {\tt EXCITON+} code. The effect of substituting combinations of N, O and S atoms, and the NH group in the molecule's ring is studied, and the role of individual molecular orbitals, many of which are found to significantly contribute to the correlation potential, quantified. Analysis of the positron bound-state Dyson orbitals shows that the positron is typically localized next to one or two of the substituents in the ring, with the order of preference N, S, O, then NH, and is also influenced by aromaticity and the presence of double ($π$) bonds in the ring.

physics.chem-ph↗

arXiv2025

Many-body theory and Gaussian-basis implementation of positron annihilation $γ$-ray spectra on polyatomic molecules

Doppler-broadened $γ$-ray spectra for positron annihilation on molecules are calculated using many-body theory. By employing Gaussian bases for the electron and positron wavefunctions, a computable expression that involves a four-centre integral over the two-annihilation-photon momenta is derived for the $γ$ spectra in the independent particle model approximation to the annihilation vertex, and implemented in the open-source {\tt EXCITON+} code. The influence of electron-positron correlations on the $γ$ spectra is examined through \textit{ab initio} treatment of the positron wavefunction, whilst corrections to the annihilation vertex are treated approximately via enhancement factors previously calculated [D. G. Green and G. F. Gribakin, Phys.~Rev.~Lett.~{\bf 114}, 093201 (2015)] exactly for atoms. Calculated $γ$ spectra for furan and acetonitrile are presented for annihilation from the positron bound state with electrons of individual molecular orbitals. For such annihilation from the positron-molecule bound state, it is found that the magnitude of the partial contribution to the $γ$ spectra from individual molecular orbitals depends not just on the orbital energies, but also on the molecular symmetry, more precisely the relative localisation of the positron and electron densities.

physics.atom-ph↗

arXiv2025

Many-body theory calculations of positron binding to parabenzoquinone

Positron binding in parabenzoquinone is studied using \textit{ab initio} many-body theory. The effects of electron-positron correlations including polarization, virtual positronium formation and positron-hole repulsion, as well as those of $π$ bonds, aromaticity, and lone electron pairs, are considered. The binding energy is calculated as 60$\pm$16 meV, considerably larger than the 0.0925 meV value inferred from recent scattering calculations of [G. Moreira and M. Bettega, {\emph{Eur.~Phys.~J.~D}} {\bf 78} (2024)], but substantially smaller than we find in benzene (148$\pm$26 meV). The positron contact density (lifetime) is calculated as 8.0$\times10^{-3}$ a.u. (2.48 ns), vs.~1.61$\times 10^{-2}$ a.u. (0.81 ns) in benzene. The decrease (increase) in binding (annihilation rate) in parabenzoquinone compared to benzene is ascribed to the loss of aromaticity: the electron density on the positive oxygen nuclei being relatively harder for the positron to probe compared to the aromatic rings in benzene.

physics.chem-ph↗

arXiv2023

Many-body Theory Calculations of Positron Binding to Halogenated Hydrocarbons

Positron binding energies in halogenated hydrocarbons are calculated \emph{ab initio} using many-body theory. For chlorinated molecules, including planars for which the interaction is highly anisotropic, very good to excellent agreement with experiment and recent DFT-based model-potential calculations is found. Predictions for fluorinated and brominated molecules are presented. The comparative effect of fluorination, chlorination and bromination is elucidated by identifying trends within molecular families including dihaloethylenes and halomethanes based on global molecular properties (dipole moment, polarizability, ionization energy). It is shown that relative to brominated and chlorinated molecules, fluorinated molecules generate a less attractive positron-molecule potential due to larger ionization energies and smaller density of molecular orbitals close to the HOMO, resulting in very weak, or in most cases loss of, positron binding. Overall, however, it is shown that the global molecular properties are not universal predictors of binding energies, exemplified by consideration of CH$_3$Cl vs.~\emph{cis.}-C$_2$H$_2$F$_2$: despite the latter having a larger dipole moment, lower ionization energy and similar polarizability its binding energy is significantly smaller (25 meV vs.~3 meV, respectively), owing to the important contribution of multiple molecular orbitals to, and the anisotropy of, the positron-molecule correlation potential.

physics.chem-ph↗

arXiv2023

Positron annihilation and binding in aromatic and other ring molecules

Annihilation spectra are presented for aromatic and heterocyclic ring molecules resolved as a function of incident positron energy using a trap-based positron beam. Comparisons with the vibrational mode spectra yield positron-molecule binding energies. Good to excellent agreement is found between the measured binding energies and the predictions of an \textit{ab initio} many-body theory that takes proper account of electron-positron correlations including virtual-positronium formation. The calculations elucidate the competition between permanent dipole moments and $π$ bonds in determining the spatial distribution of the bound-state positron density. The implications of these results and the role of multimode features in annihilation in these molecules, including Fermi resonances, are discussed.

physics.chem-ph↗

arXiv2023

Many-body theory calculations of positronic-bonded molecular dianions

The energetic stability of positron di-anion systems [A$^-;e^+;$A$^-$] is studied via many-body theory, where $A^-$ includes H$^{-}$, F$^{-}$, Cl$^{-}$ and the molecular anions (CN)$^{-}$ and (NCO)$^{-}$. Specifically, the energy of the system as a function of ionic separation is determined by solving the Dyson equation for the positron in the field of the two anions, using a positron-anion self energy as constructed in [J. Hofierka, B. Cunningham, C. M. Rawlins, C. H. Patterson and D. G. Green, \emph{Nature} {\bf 606} 688 (2022)] that accounts for correlations including polarization, screening, and virtual-positronium formation. Calculations are performed for a positron interacting with H$_{2}^{2-}$, F$_{2}^{2-}$, and Cl$_{2}^{2-}$, and are found to be in good agreement with previous theory. In particular, we confirm the presence of two minima in the potential energy of the [H$^-;e^+$;H$^-$] system with respect to ionic separation: one a positronically-bonded [H$^-;e^+$;H$^-$] local minimum at ionic separations $r\sim3.4$~Å\phantom{}, and a global minimum at smaller ionic separations $r\lesssim1.6$~Å\phantom{} that gives overall instability of the system with respect to dissociation into a H$_2$ molecule and a positronium negative ion, Ps$^-$. The first predictions are made for positronic bonding in dianions consisting of molecular anionic fragments, specifically for (CN)$_{2}^{2-}$, and (NCO)$_{2}^{2-}$. In all cases we find that the molecules formed by the creation of a positronic bond are stable relative to dissociation into A$^-$ and $e^+$A$^-$ (positron bound to a single anion), with bond energies on the order of 1~eV and bond lengths on the order of several \r angstroms.

physics.chem-ph↗

arXiv2023

Gaussian-basis many-body theory calculations of positron binding to negative ions and atoms

Positron binding energies in the negative ions H$^-$, F$^-$, Cl$^-$ and Br$^-$, and the closed-shell atoms Be, Mg, Zn and Ca, are calculated via a many-body theory approach developed by the authors [J.~Hofierka \emph{et al.} Nature~{\bf 608}, 688-693 (2022)]. Specifically, the Dyson equation is solved using a Gaussian basis, with the positron self energy constructed from three infinite classes of diagrams that account for the strong positron-atom correlations that characterise the system including the positron-induced polarization of the electron cloud, screening of the electron-positron Coulomb interaction, virtual-positronium formation and electron-hole and positron-hole interactions. For the negative ions, binding occurs at the static level of theory, and the correlations are found to enhance the binding energies by $\sim$25--50\%, yielding results in good agreement with ($\lesssim$5\% larger than) calculations from a number of distinct methods. For the atoms, for which binding is enabled exclusively by correlations, most notably virtual-Ps formation, the binding energies are found to be of similar order to (but $\sim$10--30\% larger than) relativistic coupled-cluster calculations of [C. Harabati, V.~A.~Dzuba and V.~V. Flambaum, Phys.~Rev.~A {\bf 89}, 022517 (2014)], both of which are systematically larger than stochastic variational calculations of [M.~Bromley and J.~Mitroy, Phys.~Rev.~A {\bf 73} (2005); J.~Mitroy, J.~At.~Mol.~Sci.~{\bf 1}, 275 (2010)].

physics.atom-ph↗

arXiv2023

Many-Body Theory Calculations of Positron Scattering and Annihilation in H$_2$, N$_2$ and CH$_4$

The recently developed ab initio many-body theory of positron molecule binding [J. Hofierka et al., Nature, 606, 688 (2022)] is combined with the shifted pseudostates method [A. R. Swann and G. F. Gribakin, Phys. Rev. A 101, 022702 (2020)] to calculate positron scattering and annihilation rates on small molecules, namely H$_2$, N$_2$ and CH$_4$. The important effects of positron-molecule correlations are delineated. The method provides uniformly good results for annihilation rates on all the targets, from the simplest (H$_2$, for which only a sole previous calculation agrees with experiment), to larger targets, where high-quality calculations have not been available.

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

Many-body theory of positron binding in polyatomic molecules

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 mechanisms of binding are not understood. Here, we develop a many-body theory of positron-molecule interactions and uncover the role of strong many-body correlations including polarization of the electron cloud, screening of the positron-electron Coulomb interaction by molecular electrons, and crucially, the unique non-perturbative process of virtual-positronium formation (where a molecular electron temporarily tunnels to the positron): they dramatically enhance binding in polar molecules and enable binding in nonpolars. We also elucidate the role of individual molecular orbitals, highlighting the importance of electronic $π$ bonds. Overall, we calculate binding energies in agreement with experiment (to within 1% in cases), and we predict binding in formamide and nucleobases. As well as supporting resonant annihilation experiments and positron-based molecular spectroscopy, the approach can be extended to positron scattering and annihilation $γ$ spectra in molecules and condensed matter, to provide fundamental insight and predictive capability required to properly interpret materials science diagnostics, develop antimatter-based technologies (including positron traps, beams and positron emission tomography), and understand positrons in the galaxy.

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↗

arXiv2021

Positron cooling via inelastic collisions in CF$_4$ and N$_2$ gases

Positron cooling via inelastic collisions in CF$_4$ and N$_2$ gases is simulated, including positron-positron interactions. Owing to the molecular symmetries, cooling is assumed to be chiefly due to energy loss via vibrational (rotational) excitations for CF$_4$ (N$_2$). For CF$_4$, it is found that the inclusion of the dipole-inactive $ν_1$ mode, in addition to the dipole-active modes $ν_3$ and $ν_4$, can provide room-temperature thermalization and an accurate cooling timescale. Combination cooling enabled by the $ν_1$ mode, and positron-positron interactions both contribute to the Maxwellianization of the positron momentum distribution. For both gases the evolution of the positron temperature is found to be in excellent agreement with experiment.

physics.atom-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

Positron cooling and annihilation in noble gases

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 to thermalisation: $\sim$0.1 in He, $\sim$0 in Ne (due to cooling effectively stalling in the relatively deep momentum-transfer cross-section minimum), $\sim$0.15 in Ar, $\sim$0.05 in Kr and $\sim$0.01 in Xe. For Xe, the time-varying annihilation rate $\bar{Z}_{\rm eff}(τ)$ is shown to be highly sensitive to the depletion of the distribution due to annihilation, conclusively explaining the long-standing discrepancy between gas-cell and trap-based measurements in Xe. The \emph{ab initio} calculations enable the first simultaneous probing of the energy dependence of the the scattering cross section and annihilation rate. Overall, the use of the accurate atomic data gives $\bar{Z}_{\rm eff}(τ)$ in close agreement with experiment for all noble gases except Ne, the experiment for which is proffered to have suffered from incomplete knowledge of the fraction of positrons surviving to thermalisation and/or the presence of impurities.

physics.atom-ph↗

arXiv2017

Probing positron cooling in noble gases via annihilation $γ$ 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 complementary to positron lifetime spectroscopy.

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↗