A geometric approach to decoding molecular structure and dynamics from photoionization of isotropic samples

Ordonez AF, Smirnova O (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Physical Chemistry Chemical Physics Royal Society of Chemistry

Book Volume: 24

Pages Range: 13605-13615

Journal Issue: 22

DOI: 10.1039/d1cp05645j

Abstract

We propose a geometric approach to the description and analysis of photoelectron angular distributions resulting from isotropic samples in the case of few-photon ionization by electric fields of arbitrary polarization. This approach formulates the standard photoionization observables - the bl,m expansion coefficients of the photoelectron angular distribution, in terms of geometrical properties of the vector field D⃑(k⃑) ≡ 〈k⃑|d⃑|0〉 describing the electronic transition from a bound state |0〉 into a scattering state |k⃑〉 - the photoionization transition dipole. Besides revealing selection rules for the enantio-sensitivity of bl,m coefficients in multiphoton ionization, our approach yields very compact expressions for both chiral and achiral molecules revealing how the molecular rotational invariants couple to the rotational invariants of the setup defined by the electric field polarization and the arrangement of photoelectron detectors. We apply this approach to one-photon ionization and find that the forward-backward asymmetry parameter b1,0, emerging exclusively in chiral molecules and encoded in the field B⃑(k⃑) ≡ iD⃑*(k⃑) × D⃑(k⃑), is sensitive only to the components of D⃑(k⃑) perpendicular to k⃑, while the regular asymmetry parameter b2,0 emerging in chiral and achiral molecules is sensitive only to the component of D⃑(k⃑) parallel to k⃑. Next, we analyze resonantly enhanced two-photon ionization and show that b0,0 and b1,0 can be written in terms of an effectively stretched D⃑(k⃑), and how b1,0 and b3,0 can be used to probe B⃑(k⃑).

Involved external institutions

Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie im Forschungsverbund Berlin e.V. / Max Born Institute for Nonlinear Optics and Short Pulse Spectroscopy DE Germany (DE)

How to cite

APA:

Ordonez, A.F., & Smirnova, O. (2022). A geometric approach to decoding molecular structure and dynamics from photoionization of isotropic samples. Physical Chemistry Chemical Physics, 24(22), 13605-13615. https://doi.org/10.1039/d1cp05645j

MLA:

Ordonez, Andres F., and Olga Smirnova. "A geometric approach to decoding molecular structure and dynamics from photoionization of isotropic samples." Physical Chemistry Chemical Physics 24.22 (2022): 13605-13615.

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