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ASTRA: Transition-density-matrix approach to molecular ionization

J M Randazzo, Carlos Marante, S. Chattopadhyay, Barry I. Schneider, Jeppe Olsen, Luca Argenti

2023Physical Review Research15 citationsDOIOpen Access PDF

Abstract

We describe astra (attosecond transitions), a close-coupling approach to molecular ionization that uses many-body transition-density matrices between ionic states with arbitrary spin and symmetry, in combination with hybrid integrals between Gaussian and numerical orbitals, to efficiently evaluate photoionization observables. Within the transition-density-matrix approach, the evaluation of interchannel coupling is exact and does not depend on the size of the configuration-interaction space of the ions. Thanks to these two crucial features, astra opens the way to studying highly correlated and comparatively large targets at a manageable computational cost. Here, astra is used to predict the parameters of bound and autoionizing states of the boron atom and of the ${\mathrm{N}}_{2}$ molecule, as well as the total photoionization cross section of boron, the nitrogen molecule $({\mathrm{N}}_{2})$, and formaldehyde $({\mathrm{H}}_{2}\mathrm{CO})$. Our results are in excellent agreement with theoretical and experimental values from the literature.

Topics & Concepts

ASTRAIonizationMatrix (chemical analysis)ChemistryAtomic physicsMaterials scienceChemical physicsPhysicsOrganic chemistryIonNuclear physicsChromatographyLaser-Matter Interactions and ApplicationsMass Spectrometry Techniques and ApplicationsAdvanced Chemical Physics Studies
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