Ultrafast dissipative spin-state dynamics triggered by x-ray pulse trains

Möhle, Tobias; Kühn, Oliver; Bokarev, Sergey I.

doi:10.1103/physreva.98.013408

Cited by 11 publications

(18 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Due to their correlated nature, they not only probe but also initiate or compete with intricate ultrafast electronic and nuclear dynamics e.g. [8][9][10][11][12]. Additionally, they provide the main channel for the decay of core vacancies [13] and play a key role in biological radiation damage, creating * sergey.bokarev@uni-rostock.de highly charged cations while a cascade of highly reactive low energy electrons is emitted [11,[14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Multireference quantum chemistry protocol for simulating autoionization spectra: Test of ionization continuum models for the neon atom

2019

Self Cite

View full text Add to dashboard Cite

In this contribution we present a protocol to evaluate partial and total Auger decay rates combining the restricted active space self-consistent field electronic structure method for the bound part and numerically obtained continuum orbitals in the single-channel scattering theory framework. On top of that, the two-step picture is employed to evaluate the partial rates. The performance of the method is exemplified for the prototypical Auger decay of the neon 1s −1 3p resonance. Different approximations to obtain the continuum orbitals, the partial rate matrix elements, and the electronic structure of the bound part are tested against theoretical and experimental reference data. It is demonstrated that the partial and total rates are most sensitive to the accuracy of the continuum orbital. For instance, it is necessary to account for the true direct Coulomb potential of the ion for the determination of the continuum wave functions. The Auger energies, however, can be reproduced quite well already with a rather small active space. Finally, perspectives of the application of the proposed protocol to molecular systems are discussed. arXiv:1905.05785v1 [physics.chem-ph]

show abstract

Section: Introductionmentioning

confidence: 99%

Multireference quantum chemistry protocol for simulating autoionization spectra: Test of ionization continuum models for the neon atom

2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…For instance, the approach implemented within the RhoDyn module has been used to study spin dynamics for excitation at the L-edge of transition metal complexes. 43,58,59,91 We continue discussing these applications here, shifting the focus to methodological issues. The process under study can be understood as follows: After absorption of an X-ray photon, the localized core-hole is created.…”

Section: Ultrafast Spin-flip Dynamicsmentioning

confidence: 99%

RhoDyn: a $ρ$-TD-RASCI framework to study ultrafast electron dynamics in molecules

Kochetov¹,

Bokarev²

2021

Preprint

Self Cite

View full text Add to dashboard Cite

This article presents the program module RhoDyn as part of the OpenMOLCAS project intended to study ultrafast electron dynamics within the density-matrix-based timedependent restricted active space configuration interaction framework (ρ-TD-RASCI).The formalism allows for the treatment of spin-orbit coupling effects, accounts for nuclear vibrations in the form of a vibrational heat-bath, and naturally incorporates (auto)ionization effects. Apart from describing the theory behind and the program workflow, the paper also contains examples of its application to the simulations of the linear L 2,3 absorption spectra of titanium complex, high harmonic generation in the hydrogen molecule, ultrafast charge migration in benzene and iodoacetylene, and spin-flip dynamics in the core-excited states of iron complexes.

show abstract

“…For Fe 3+ , for instance, it has been found that the low‐energy part of the L 3 ‐edge is dominated by t 2 g ‐type transitions . The multiplicity of the core‐excited states strongly depends on energy . For energies up to about the L 3 maximum spin‐conserving quintet–quintet transition dominate.…”

Section: Applicationsmentioning

confidence: 99%

“…Analysis of inelastic RIXS spectra revealed that for all species most features are due to spin‐forbidden transitions, mediated by core‐excited states similar to what has been discussed for the iron complex in Section 4.1. Note that intricate spin mixing of the core‐excited state gives rise to the exciting ultrafast spin‐flip dynamics which can be triggered by XFEL and HHG X‐ray pulses …”

Section: Applicationsmentioning

confidence: 99%

See 1 more Smart Citation

Theoretical X‐ray spectroscopy of transition metal compounds

Bokarev

Kühn

2019

WIREs Comput Mol Sci

Self Cite

View full text Add to dashboard Cite

X-ray spectroscopy is one of the most powerful tools to access structure and properties of matter in different states of aggregation as it allows to trace atomic and molecular energy levels in course of various physical and chemical processes. Xray spectroscopic techniques probe the local electronic structure of a particular atom in its environment, in contrast to ultraviolet/visible (UV/Vis) spectroscopy, where transitions generally occur between delocalized molecular orbitals. Complementary information is provided by using a combination of different absorption, emission, scattering as well as photo-and autoionization X-ray methods. However, interpretation of the complex experimental spectra and verification of experimental hypotheses is a nontrivial task and powerful first principles theoretical approaches that allow for a systematic investigation of a broad class of systems are needed. Focusing on transition metal compounds, L-edge spectra are of particular relevance as they probe the frontier d-orbitals involved in metal-ligand bonding. Here, neardegeneracy effects in combination with spin-orbit coupling lead to a complicated multiplet energy level structure, which poses a serious challenge to quantum chemical methods. Multiconfigurational self-consistent field (MCSCF) theory has been shown to be capable of providing a rather detailed understanding of experimental X-ray spectroscopy. However, it cannot be considered as a "blackbox" tool and its application requires not only a command of formal theoretical aspects, but also a broad knowledge of already existing applications. Both aspects are covered in this overview.

show abstract

Ultrafast dissipative spin-state dynamics triggered by x-ray pulse trains

Abstract: Here,Ĥ S (t) describes the relevant system, i.e. that part of the electronic degrees of freedom (DOF) whose dynamics is triggered by the X-ray light. The relevant system arXiv:1806.06262v1 [quant-ph]

Cited by 11 publications

References 33 publications

Multireference quantum chemistry protocol for simulating autoionization spectra: Test of ionization continuum models for the neon atom

Multireference quantum chemistry protocol for simulating autoionization spectra: Test of ionization continuum models for the neon atom

RhoDyn: a $ρ$-TD-RASCI framework to study ultrafast electron dynamics in molecules

Theoretical X‐ray spectroscopy of transition metal compounds

Contact Info

Product

Resources

About