Simulated and Experimental Time-Resolved Photoelectron Spectra of the Intersystem Crossing Dynamics in 2-Thiouracil

Mai, Sebastian; Mohamadzade, Abed; Marquetand, Philipp; González, Leticia; Ullrich, Susanne

doi:10.3390/molecules23112836

Cited by 35 publications

(42 citation statements)

References 70 publications

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“…Our results are consistent with an extensive body of prior work, which makes use of the Dyson method for calculating photoelectron spectra [101][102][103][104]. The Dyson approach has also been used to calculate photoelectron spectra away from the Franck-Condon point in several earlier time-resolved photoelectron spectroscopy studies [18,19,81,[105][106][107].…”

Section: Trajectory Surface Hopping Calculationsupporting

confidence: 86%

Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

et al. 2020

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Pump-probe measurements aim to capture the motion of electrons and nuclei on their natural timescales (femtoseconds to attoseconds) as chemical and physical transformations take place, effectively making "molecular movies" with short light pulses. However, the quantum dynamics of interest are filtered by the coordinate-dependent matrix elements of the chosen experimental observable. Thus, it is only through a combination of experimental measurements and theoretical calculations that one can gain insight into the internal dynamics. Here, we report on a combination of structural (relativistic ultrafast electron diffraction, or UED) and spectroscopic (time-resolved photoelectron spectroscopy, or TRPES) measurements to follow the coupled electronic and nuclear dynamics involved in the internal conversion and photodissociation of the polyatomic molecule, diiodomethane (CH 2 I 2). While UED directly probes the 3D nuclear dynamics, TRPES only serves as an indirect probe of nuclear dynamics via Franck-Condon factors, but it is sensitive to electronic energies and configurations, via Koopmans' correlations and photoelectron angular distributions. These two measurements are interpreted with trajectory surface hopping calculations, which are capable of simulating the observables for both measurements from the same dynamics calculations. The measurements highlight the nonlocal dynamics captured by different groups of trajectories in the calculations. For the first time, both UED and TRPES are combined with theory capable of calculating the observables in both cases, yielding a direct view of the structural and nonadiabatic dynamics involved.

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Section: Trajectory Surface Hopping Calculationsupporting

confidence: 86%

Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

et al. 2020

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“…Eventually, the population is trapped in the lowest triplet state in each channel ( 3 ππ*/ 3 ππ*′). Our calculations strongly suggest the involvement of the dark nπ*/nπ*′ states in the non‐adiabatic decay, in agreement with a previous dynamical calculation and time‐resolved photoelectron spectroscopy experiments in the gas phase . Nonetheless, the fingerprint PA signals of the nπ*/nπ*′ states are either weak in intensity (e.g., 24TU; for more details see Figures S6 and S7 in the Supporting Information) or coincide with more intense PA signals coming from the ππ*/ππ*′ states and the triplet manifold (e.g., 2TU; Figure S4, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils

Teles-Ferreira

Conti

Borrego-Varillas

et al. 2019

Chemistry A European J

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Photoinduced processes in thiouracil derivatives have lately attracted considerable attention due to their suitability for innovative biological and pharmacological applications. Here, sub‐20 fs broadband transient absorption spectroscopy in the near‐UV are combined with CASPT2/MM decay path calculations to unravel the excited‐state decay channels of water solvated 2‐thio and 2,4‐dithiouracil. These molecules feature linear absorption spectra with overlapping ππ* bands, leading to parallel decay routes which we systematically track for the first time. The results reveal that different processes lead to the triplet states population, both directly from the ππ* absorbing state and via the intermediate nπ* dark state. Moreover, the 2,4‐dithiouracil decay pathways is shown to be strongly correlated either to those of 2‐ or 4‐thiouracil, depending on the sulfur atom on which the electronic transition localizes.

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“…Ausd iesem Grund ist es erforderlich, dass nichtadiabatische Dynamiksimulationen einen Schritt weiter gehen und explizit spektroskopische Observablen berechnen, also transiente Absorptionsspektren, Photoelektronenspektren und andere.A uch wenn in einem Großteil der Dynamiksimulationen angeregter Zustände keine Observablen berechnet werden, ist es durchaus mçglich, zeitaufgelçste Photoelektronenspektren zu simulieren. Beispiele dafürs ind Untersuchungen von Aceton, [202] Uracil, [203] 2-Thiouracil [204] (Abbildung 6a)o der kleiner Metallatomcluster. [205] Simulationen von zeitaufgelçsten Fluoreszenzspektren wurden beispielsweise fürA zobenzol [206] durchgeführt, während füre inen Rhenium-Übergangsmetallkomplex auch Simulationen von zeitaufgelçsten Lumineszenzspektren [11] verçffentlicht wurden (Abbildung 6b).…”

Section: Simulation Von Observablenunclassified

“…a) Vergleich der experimentellen (links) und simulierten (rechts) zeitaufgelçsten Photoelektronenspektren von 2-Thiouracil.M it Genehmigung adaptiert von Lit. [204].b)Experimentelle (oben) und simulierte (unten) zeitaufgelçste Lumineszenzspektren von [Re(CO) 3 (Imidazol)(Phenanthrolin)] + .Mit Genehmigung adaptiert von Lit. [11].c)V ergleich experimenteller (oben) und simulierter( unten) Attosekunden-aufgelçster transienter Absorptionsspektren von Methylbromid.…”

Section: Simulation Von Observablenunclassified

Molekulare Photochemie: Moderne Entwicklungen in der theoretischen Chemie

Mai

González

2020

Angewandte Chemie

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Photochemie ist ein faszinierendes Teilgebiet der Chemie, das sich mit der Wechselwirkung von Molekülen und Licht befasst. Die Simulation von lichtinduzierten Prozessen spielt auch in anderen Forschungsgebieten wie Biologie, Materialwissenschaften oder Medizin eine bedeutende Rolle. Dieser Kurzaufsatz beleuchtet die jüngsten Entwicklungen in der theoretischen Chemie, die das Ziel haben, experimentelle Genauigkeit bei der Berechnung von elektronisch angeregten Zuständen von Molekülen und bei der Simulation von deren lichtinduzierten Dynamiken zu erreichen. Wir konzentrieren uns dabei auf neue, aufstrebende Methoden und zeigen ausgewählte Beispiele, welche die Fortschritte der letzten Jahre für folgende Themen aufzeigen: die Voraussage komplexer Elektronenstrukturen mit starker Korrelation, die Berechnung von großen Molekülen, die Beschreibung von multi‐chromophorischen Systemen und die Simulation nicht‐adiabatischer Moleküldynamik auf langen Zeitskalen; dies umfasst Moleküle sowohl in der Gasphase als auch in komplexer biologischer Umgebung.

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Simulated and Experimental Time-Resolved Photoelectron Spectra of the Intersystem Crossing Dynamics in 2-Thiouracil

Cited by 35 publications

References 70 publications

Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils

Molekulare Photochemie: Moderne Entwicklungen in der theoretischen Chemie

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