Variational surface matching for multichannel molecular photoionization
Abstract
We present an improved method for computing multichannel scattering states in the \ASTRA{} (AttoSecond TRAnsitions) molecular ionization code. Our pole-free Galerkin method with variational surface matching (PFG-VSM) yields a boundary response that is stationary with respect to errors in the interior wave function. Compared with matching based on directly evaluated radial derivatives, this formulation yields substantially faster convergence and greater numerical stability as the number of open channels increases. Comparison with a numerical solution of the exactly separable H2+ problem establishes the accuracy attainable in a hybrid Gaussian--B-spline basis for a polycentric potential, independently of many-electron close-coupling approximations. A direct comparison of the two matching prescriptions for CO demonstrates the stability of the variational formulation under radial-basis coarsening. For neon, agreement with the NewStock atomic ionization code tests the treatment of the continuum degeneracies that arise when rotational symmetry is represented in D2h. The excellent agreement with the independent \XCHEM{} molecular ionization code for CO partial cross sections and molecular-frame photoelectron angular distributions, both away from and across resonances, is a strong confirmation of the correctness of both codes. A comparison for pyrazine extends this validation to a larger polyatomic target.
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BibTeX
@misc{marante2026variational,
title = {{Variational surface matching for multichannel molecular photoionization}},
author = {Carlos Marante and Vicent J Borràs and Jesús González Vázquez and Fernando Martín and Luca Argenti},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.40953},
eprint = {2610.40953},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.40953},
}
RIS
TY - UNPB
TI - Variational surface matching for multichannel molecular photoionization
AU - Carlos Marante
AU - Vicent J Borràs
AU - Jesús González Vázquez
AU - Fernando Martín
AU - Luca Argenti
PY - 2026
DA - 2026/10/29
PB - arXiv
DO - 10.48550/arxiv.2610.40953
UR - https://arxiv.org/abs/2610.40953
AB - We present an improved method for computing multichannel scattering states in the \ASTRA{} (AttoSecond TRAnsitions) molecular ionization code. Our pole-free Galerkin method with variational surface matching (PFG-VSM) yields a boundary response that is stationary with respect to errors in the interior wave function. Compared with matching based on directly evaluated radial derivatives, this formulation yields substantially faster convergence and greater numerical stability as the number of open channels increases. Comparison with a numerical solution of the exactly separable H_2^+ problem establishes the accuracy attainable in a hybrid Gaussian--B-spline basis for a polycentric potential, independently of many-electron close-coupling approximations. A direct comparison of the two matching prescriptions for CO demonstrates the stability of the variational formulation under radial-basis coarsening. For neon, agreement with the NewStock atomic ionization code tests the treatment of the continuum degeneracies that arise when rotational symmetry is represented in D_2h. The excellent agreement with the independent \XCHEM{} molecular ionization code for CO partial cross sections and molecular-frame photoelectron angular distributions, both away from and across resonances, is a strong confirmation of the correctness of both codes. A comparison for pyrazine extends this validation to a larger polyatomic target.
ER -