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Molecular Quantum Dynamics Beyond Bound States
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Molecular Quantum Dynamics Beyond Bound States

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Physical Chemistry".

Deadline for manuscript submissions: closed (31 October 2022) | Viewed by 16326

Special Issue Editor

Dr. Sergey I. Bokarev

E-Mail Website
Guest Editor
Universität Rostock, Rostock, Germany
Interests: electronic structure theory; quantum chemistry; density functional theory; excited states; ionization and autoionization; theoretical x-ray spectroscopy; ultrafast dynamics; transition metals; photocatalysis

Special Issue Information

Dear Colleagues,

The photon-in/electron-out processes provide a wealth of information about the electronic structure of the target system, which is encoded in the kinetic energy of the outgoing electron, its angular distribution, spin-polarization, etc. That is why different flavors of steady-state and time-resolved photoemission and Auger spectroscopies enjoy great popularity in studying molecules. This Special Issue will address theoretical methods to describe various aspects of ionization and autoionization spectroscopies from UV/Vis to X-ray domains, the interaction of molecules and atoms with intense laser fields, as well as the electronic and non-adiabatic dynamics following the expulsion of an electron. Articles presenting new methodological developments and applications to molecular spectroscopy and dynamics are welcome.

Dr. Sergey I. Bokarev
Guest Editor

Manuscript Submission Information

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Keywords

  • Photoemission 
  • Auger decay
  • Charge migration 
  • High harmonic generation
  • Ultrafast dynamics

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Published Papers (7 papers)

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Research

20 pages, 2716 KiB  
Article
Valence and Core Photoelectron Spectra of Aqueous I3− from Multi-Reference Quantum Chemistry
by Vladislav Kochetov, Md Sabbir Ahsan, Dennis Hein, Iain Wilkinson and Sergey I. Bokarev
Molecules 2023, 28(14), 5319; https://doi.org/10.3390/molecules28145319 - 10 Jul 2023
Viewed by 1468
Abstract
The I3− molecule is known to undergo substantial structural reorganization upon solvation by a protic solvent, e.g., water. However, the details of this process are still controversially discussed in the literature. In the present study, we combined experimental and theoretical efforts [...] Read more.
The I3− molecule is known to undergo substantial structural reorganization upon solvation by a protic solvent, e.g., water. However, the details of this process are still controversially discussed in the literature. In the present study, we combined experimental and theoretical efforts to disentangle this controversy. The valence (5p), N4,5 (4d), and M4,5 (3d) edge photoelectron spectra were measured in an aqueous solution and computed using high-level multi-reference methods. Our previous publication mainly focused on obtaining reliable experimental evidence, whereas in the present article, we focused primarily on theoretical aspects. The complex electronic structure of I3− requires the inclusion of both static and dynamic correlation, e.g., via the multi-configurational perturbation theory treatment. However, the resulting photoelectron spectra appear to be very sensitive to problems with variational stability and intruder states. We attempted to obtain artifact-free spectra, allowing for a more reliable interpretation of experiments. Finally, we concluded that the 3d Photoelectron Spectrum (PES) is particularly informative, evidencing an almost linear structure with a smaller degree of bond asymmetry than previously reported. Full article
(This article belongs to the Special Issue Molecular Quantum Dynamics Beyond Bound States)
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23 pages, 4311 KiB  
Article
Three-Electron Dynamics of the Interparticle Coulombic Decay in Doubly Excited Clusters with One-Dimensional Continuum Confinement
by Joana-Lysiane Schäfer, Fabian Langkabel and Annika Bande
Molecules 2022, 27(24), 8713; https://doi.org/10.3390/molecules27248713 - 9 Dec 2022
Cited by 1 | Viewed by 1298
Abstract
A detailed analysis of the electronic structure and decay dynamics in a symmetric system with three electrons in three linearly aligned binding sites representing quantum dots (QDs) is given. The two outer A QDs are two-level potentials and can act as (virtual) photon [...] Read more.
A detailed analysis of the electronic structure and decay dynamics in a symmetric system with three electrons in three linearly aligned binding sites representing quantum dots (QDs) is given. The two outer A QDs are two-level potentials and can act as (virtual) photon emitters, whereas the central B QD can be ionized from its one level into a continuum confined on the QD axis upon absorbing virtual photons in the inter-Coulombic decay (ICD) process. Two scenarios in such an ABA array are explored. One ICD process is from a singly excited resonance state, whose decay releasing one virtual photon we find superimposed with resonance energy transfer among both A QDs. Moreover, the decay-process manifold for a doubly excited (DE) resonance is explored, in which collective ICD among all three sites and excited ICD among the outer QDs engage. Rates for all processes are found to be extremely low, although ICD rates with two neighbors are predicted to double compared to ICD among two sites only. The slowing is caused by Coulomb barriers imposed from ground or excited state electrons in the A sites. Outliers occur on the one hand at short distances, where the charge transfer among QDs mixes the possible decay pathways. On the other hand, we discovered a shape resonance-enhanced DE-ICD pathway, in which an excited and localized B* shape resonance state forms, which is able to decay quickly into the final ICD continuum. Full article
(This article belongs to the Special Issue Molecular Quantum Dynamics Beyond Bound States)
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30 pages, 2887 KiB  
Article
Exact Factorization Adventures: A Promising Approach for Non-Bound States
by Evaristo Villaseco Arribas, Federica Agostini and Neepa T. Maitra
Molecules 2022, 27(13), 4002; https://doi.org/10.3390/molecules27134002 - 22 Jun 2022
Cited by 14 | Viewed by 3073
Abstract
Modeling the dynamics of non-bound states in molecules requires an accurate description of how electronic motion affects nuclear motion and vice-versa. The exact factorization (XF) approach offers a unique perspective, in that it provides potentials that act on the nuclear subsystem or electronic [...] Read more.
Modeling the dynamics of non-bound states in molecules requires an accurate description of how electronic motion affects nuclear motion and vice-versa. The exact factorization (XF) approach offers a unique perspective, in that it provides potentials that act on the nuclear subsystem or electronic subsystem, which contain the effects of the coupling to the other subsystem in an exact way. We briefly review the various applications of the XF idea in different realms, and how features of these potentials aid in the interpretation of two different laser-driven dissociation mechanisms. We present a detailed study of the different ways the coupling terms in recently-developed XF-based mixed quantum-classical approximations are evaluated, where either truly coupled trajectories, or auxiliary trajectories that mimic the coupling are used, and discuss their effect in both a surface-hopping framework as well as the rigorously-derived coupled-trajectory mixed quantum-classical approach. Full article
(This article belongs to the Special Issue Molecular Quantum Dynamics Beyond Bound States)
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21 pages, 1076 KiB  
Article
Continuum Electronic States: The Tiresia Code
by Piero Decleva, Mauro Stener and Daniele Toffoli
Molecules 2022, 27(6), 2026; https://doi.org/10.3390/molecules27062026 - 21 Mar 2022
Cited by 9 | Viewed by 2258
Abstract
A multicenter (LCAO) B-spline basis is described in detail, and its capabilities concerning affording convergent solutions for electronic continuum states and wavepacket propagation are presented. It forms the core of the Tiresia code, which implements static-DFT and TDDFT hamiltonians, as well as single [...] Read more.
A multicenter (LCAO) B-spline basis is described in detail, and its capabilities concerning affording convergent solutions for electronic continuum states and wavepacket propagation are presented. It forms the core of the Tiresia code, which implements static-DFT and TDDFT hamiltonians, as well as single channel Dyson-DFT and Dyson-TDDFT descriptions to include correlation in the bound states. Together they afford accurate and computationally efficient descriptions of photoionization properties of complex systems, both in the single photon and strong field environments. A number of examples are provided. Full article
(This article belongs to the Special Issue Molecular Quantum Dynamics Beyond Bound States)
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12 pages, 3324 KiB  
Article
Discrimination of Excited States of Acetylacetone through Theoretical Molecular-Frame Photoelectron Angular Distributions
by Aurora Ponzi, Marin Sapunar, Nadja Došlić and Piero Decleva
Molecules 2022, 27(6), 1811; https://doi.org/10.3390/molecules27061811 - 10 Mar 2022
Viewed by 2674
Abstract
Photoelectron angular distribution (PAD) in the laboratory frame for randomly oriented molecules is typically described by a single anisotropy parameter, the so-called asymmetry parameter. However, especially from a theoretical perspective, it is more natural to consider molecular photoionization by using a molecular frame. [...] Read more.
Photoelectron angular distribution (PAD) in the laboratory frame for randomly oriented molecules is typically described by a single anisotropy parameter, the so-called asymmetry parameter. However, especially from a theoretical perspective, it is more natural to consider molecular photoionization by using a molecular frame. The molecular frame PADs (MFPADs) may be used to extract information about the electronic structure of the system studied. In the last decade, significant experimental efforts have been directed to MFPAD measurements. MFPADs are highly characterizing signatures of the final ionic states. In particular, they are very sensitive to the nature of the final state, which is embodied in the corresponding Dyson orbital. In our previous work on acetylacetone, a prototype system for studying intra-molecular hydrogen bond interactions, we followed the dynamics of the excited states involved in the photoexcitation–deexcitation process of this molecule. It remains to be explored the possibility of discriminating between different excited states through the MFPAD profiles. The calculation of MFPADs to differentiate excited states can pave the way to the possibility of a clear discrimination for all the cases where the recognition of excited states is otherwise intricate. Full article
(This article belongs to the Special Issue Molecular Quantum Dynamics Beyond Bound States)
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18 pages, 653 KiB  
Article
Photoionization Observables from Multi-Reference Dyson Orbitals Coupled to B-Spline DFT and TD-DFT Continuum
by Bruno Nunes Cabral Tenorio, Aurora Ponzi, Sonia Coriani and Piero Decleva
Molecules 2022, 27(4), 1203; https://doi.org/10.3390/molecules27041203 - 10 Feb 2022
Cited by 12 | Viewed by 2418
Abstract
We present a theoretical model to compute the accurate photoionization dynamical parameters (cross-sections, asymmetry parameters and orbital, or cross-section, ratios) from Dyson orbitals obtained with the multi-state complete active space perturbation theory to the second order (MS-CASPT2) method. Our new implementation of Dyson [...] Read more.
We present a theoretical model to compute the accurate photoionization dynamical parameters (cross-sections, asymmetry parameters and orbital, or cross-section, ratios) from Dyson orbitals obtained with the multi-state complete active space perturbation theory to the second order (MS-CASPT2) method. Our new implementation of Dyson orbitals in OpenMolcas takes advantage of the full Abelian symmetry point group and has the corrected normalization. The Dyson orbitals are coupled to an accurate description of the electronic continuum obtained with a multicentric B-spline basis at the DFT and TD-DFT levels. Two prototype diatomic molecules, i.e., CS and SiS, have been chosen due to their smallness, which hides important correlation effects. These effects manifest themselves in the appearance of well-characterized isolated satellite bands in the middle of the valence region. The rich satellite structures make CS and SiS the perfect candidates for a computational study based on our highly accurate MS-CASPT2/B-spline TD-DFT protocol. Full article
(This article belongs to the Special Issue Molecular Quantum Dynamics Beyond Bound States)
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18 pages, 467 KiB  
Article
Approximate Atomic Green Functions
by Stephan Fritzsche and Andrey Surzhykov
Molecules 2021, 26(9), 2660; https://doi.org/10.3390/molecules26092660 - 1 May 2021
Cited by 7 | Viewed by 2032
Abstract
In atomic and many-particle physics, Green functions often occur as propagators to formally represent the (integration over the) complete spectrum of the underlying Hamiltonian. However, while these functions are very crucial to describing many second- and higher-order perturbation processes, they have hardly been [...] Read more.
In atomic and many-particle physics, Green functions often occur as propagators to formally represent the (integration over the) complete spectrum of the underlying Hamiltonian. However, while these functions are very crucial to describing many second- and higher-order perturbation processes, they have hardly been considered and classified for complex atoms. Here, we show how relativistic (many-electron) Green functions can be approximated and systematically improved for few- and many-electron atoms and ions. The representation of these functions is based on classes of virtual excitations, or so-called excitation schemes, with regard to given bound-state reference configurations, and by applying a multi-configuration Dirac-Hartree-Fock expansion of all atomic states involved. A first implementation of these approximate Green functions has been realized in the framework of Jac, the Jena Atomic Calculator, and will facilitate the study of various multi-photon and/or multiple electron (emission) processes. Full article
(This article belongs to the Special Issue Molecular Quantum Dynamics Beyond Bound States)
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