Steering the outcome of a photochemical reaction - An in silico experiment on the H                         2                         CSO sulfine using few-femtosecond dump pulses

Benoit Mignolet; Basile F.E. Curchod

doi:10.1063/1.5089124

Steering the outcome of a photochemical reaction - An in silico experiment on the H ₂ CSO sulfine using few-femtosecond dump pulses

Benoit Mignolet, Basile F.E. Curchod

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

3 Citations (Scopus)

Abstract

We propose a pump-dump control scheme using sub-10 fs pulses to enhance the photochemical formation of the three-membered C-S-O ring oxathiirane from the parent H ₂ CSO sulfine molecule. The ultrashort nature of the pulses is essential to promptly alter the photoinduced dynamics, e.g., while a bond is elongating, which is key to selectively form the oxathiirane by radiative dumping. We carried out an in silico pump-dump experiment with excited-state dynamics simulations that include the interaction with electric field of the pump and dump pulses. By applying the dump pulse when the CS bond is elongating, the population transferred to the ground state will form the oxathiirane with a branching ratio of 4, much higher than the one solely due to nonradiative relaxation (0.66). The overall oxathiirane yield can be increased by up to 17% when the 6 fs IR dump pulse is applied at a delay time of 47 fs.

Original language	English
Article number	101101
Journal	Journal of Chemical Physics
Volume	150
Issue number	10
DOIs	https://doi.org/10.1063/1.5089124
Publication status	Published - 14 Mar 2019

Bibliographical note

Funding Information:
B.M. acknowledges support from the Fonds National de la Recherche Scientifique, Belgium (F.R.S.-FNRS) and the University of Liège. Computational resources have been provided by the Consortium des Equipements de Calcul Intensif (CECI), funded by the F.R.S.-FNRS under Grant No. 2.5020.11. This work also made use of the facilities of the Hamilton HPC Service of Durham University.

Publisher Copyright:
© 2019 Author(s).

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Cite this

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title = "Steering the outcome of a photochemical reaction - An in silico experiment on the H 2 CSO sulfine using few-femtosecond dump pulses",

abstract = " We propose a pump-dump control scheme using sub-10 fs pulses to enhance the photochemical formation of the three-membered C-S-O ring oxathiirane from the parent H 2 CSO sulfine molecule. The ultrashort nature of the pulses is essential to promptly alter the photoinduced dynamics, e.g., while a bond is elongating, which is key to selectively form the oxathiirane by radiative dumping. We carried out an in silico pump-dump experiment with excited-state dynamics simulations that include the interaction with electric field of the pump and dump pulses. By applying the dump pulse when the CS bond is elongating, the population transferred to the ground state will form the oxathiirane with a branching ratio of 4, much higher than the one solely due to nonradiative relaxation (0.66). The overall oxathiirane yield can be increased by up to 17% when the 6 fs IR dump pulse is applied at a delay time of 47 fs. ",

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Steering the outcome of a photochemical reaction - An in silico experiment on the H ₂ CSO sulfine using few-femtosecond dump pulses. / Mignolet, Benoit; Curchod, Basile F.E.
In: Journal of Chemical Physics, Vol. 150, No. 10, 101101, 14.03.2019.

Research output: Contribution to journal › Article (Academic Journal) › peer-review

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N2 - We propose a pump-dump control scheme using sub-10 fs pulses to enhance the photochemical formation of the three-membered C-S-O ring oxathiirane from the parent H 2 CSO sulfine molecule. The ultrashort nature of the pulses is essential to promptly alter the photoinduced dynamics, e.g., while a bond is elongating, which is key to selectively form the oxathiirane by radiative dumping. We carried out an in silico pump-dump experiment with excited-state dynamics simulations that include the interaction with electric field of the pump and dump pulses. By applying the dump pulse when the CS bond is elongating, the population transferred to the ground state will form the oxathiirane with a branching ratio of 4, much higher than the one solely due to nonradiative relaxation (0.66). The overall oxathiirane yield can be increased by up to 17% when the 6 fs IR dump pulse is applied at a delay time of 47 fs.

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