R-Matrix incorporating Time (RMT) method for H2+ in short and intense laser fields

TL;DR

This paper introduces an ab initio R-Matrix incorporating Time (RMT) method adapted for the molecular hydrogen ion (H2+) to accurately simulate its behavior under intense short laser pulses, extending atomic approaches to diatomic molecules.

Contribution

The study develops a detailed theoretical RMT approach for H2+ in the Born-Oppenheimer approximation, enabling efficient and accurate solutions to the time-dependent Schrödinger Equation for diatomic molecules.

Findings

Results are independent of the artificial boundary-surface.

The method accurately reproduces experimental observables.

It offers a computationally efficient alternative to basis-set approaches.

Abstract

In this work we develop an approach for a molecular hydrogen ion (H2+) in the Born-Oppenheimer approximation while exposed to intense short-pulse radiation. Our starting point is the R-Matrix incorporating Time (RMT) formulation for atomic hydrogen [L. A. A. Nikolopoulos et al, Phys. Rev. A 78, 063420 (2008)] which has proven to be successful at treating multi-electron atomic systems efficiently and to high accuracy [L. R. Moore et al J. Mod. Opt. 58,1132, (2011)]. The present study on H2+ has been performed with a similar objective of developing an ab initio method for solving the Time-dependent Schr\"odinger Equation (TDSE) for multi-electron diatomic molecules exposed to an external time-dependent potential field. The theoretical formulation is developed in detail for the molecular hydrogen ion where all the multi-electron and inter-nuclei complications are absent. As in the atomic case, the configuration space of the electron's coordinates are separated artificially over two regions; the inner (I) and outer (II) regions. In the region I the time-dependent wavefunction is expanded on the eigenstate basis corresponding to the molecule's Hamiltonian augmented by Bloch operators, while in region II a grid representation is used. We demonstrate the independence of our results on the introduced artificial boundary-surface by calculating observables that are directly accessed experimentally and also by showing gauge-dependent quantities are also invariant with the region I box size. We also compare with other theoretical works and emphasize cases where basis-set approaches are currently very computationally expensive or intractable in terms of computational resources.