Dissipation and dynamics in ultrafast intersystem crossings

van Veenendaal, Michel

doi:10.1063/1.5125005

Title: Dissipation and dynamics in ultrafast intersystem crossings

Journal Article · Wed Jan 08 00:00:00 EST 2020 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5125005· OSTI ID:1660553

^[1]

Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

The effects of dynamics and dissipation on ultrafast intersystem crossings are studied for a dissipative two-level system coupled to a local vibronic mode. A method of amplitude damping of the wave packet is presented that accounts better for the position of the wave packet and avoids spurious transitions between potential wells. In this work, it is demonstrated that Fermi's golden rule, the typical semiquantitative approach to extract population transfer rates from potential landscapes, only holds under limited conditions. Generally, the effects of dynamics and dissipation lead to deviations from the expected exponential population transfer, strong changes in transfer times and total population transfer, and significant recurrence or "spill back" of the wave packet.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE

Grant/Contract Number:: AC02-06CH11357; FG02-03ER46097

OSTI ID:: 1660553

Alternate ID(s):: OSTI ID: 1581669

Journal Information:: Journal of Chemical Physics, Vol. 152, Issue 2; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 2 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Quantum chemical dynamics
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Title: Dissipation and dynamics in ultrafast intersystem crossings

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