Correspondence between the surface integral and linear combination of atomic orbitals methods for ionic-covalent interactions in mutual neutralisation processes involving H$^-$/D$^-$

TL;DR

This paper investigates the surface integral method for ionic-covalent interactions in mutual neutralisation, identifies a key correction factor for H$^-$ systems, and demonstrates improved agreement with experiments and other methods.

Contribution

The study reveals a necessary correction factor in the surface integral method for H$^-$, aligning it with LCAO results and experimental data, and clarifies their asymptotic equivalence.

Findings

Corrected the asymptotic wavefunction constant for H$^-$, improving accuracy.

Demonstrated the same asymptotic behaviour for surface integral and LCAO methods.

Enhanced agreement of the surface integral method with experimental results.

Abstract

The surface integral method for estimating ionic-covalent interactions in diatomic systems been successful in producing cross sections for mutual neutralisation (MN) in reasonable agreement with experimental results for branching fractions between final states in systems such as O$^+$/O$^-$ and N$^+$/O$^-$. However, for simpler cases of MN involving H$^-$ or D$^-$, such as Li$^+$/D$^-$ and Na$^+$/D$^-$, it has not produced results that are in agreement with experiments and other theoretical calculations; in particular, for Li$^+$/D$^-$ calculations predict the wrong ordering of importance of final channels, including the incorrect most populated channel. The reason for this anomaly is investigated and a leading constant to the asymptotic H$^-$ wavefunction is found that is different by roughly a factor $1/\sqrt{2}$ to that which has been used in previous calculations with the surface integral method involving H$^-$ or D$^-$. With this correction, far better agreement with both experimental results and with calculations with full quantum and LCAO methods is obtained. Further, it is shown that the surface integral method and LCAO methods have the same asymptotic behaviour, in contrast to previous claims. This result suggests the surface integral method, which is comparatively easy to calculate, has greater potential for estimating MN processes than earlier comparisons had suggested.