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Time-Resolved Femtosecond Stimulated Raman Spectra and DFT Anharmonic Vibrational Analysis of an Electronically Excited Rhenium Photosensitizer

The result's identifiers

  • Result code in IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F20%3A00522634" target="_blank" >RIV/61388955:_____/20:00522634 - isvavai.cz</a>

  • Alternative codes found

    RIV/86652036:_____/20:00522634 RIV/68378271:_____/20:00522634 RIV/60461373:22310/20:43920809

  • Result on the web

    <a href="http://hdl.handle.net/11104/0307098" target="_blank" >http://hdl.handle.net/11104/0307098</a>

  • DOI - Digital Object Identifier

    <a href="http://dx.doi.org/10.1021/acs.jpca.9b10840" target="_blank" >10.1021/acs.jpca.9b10840</a>

Alternative languages

  • Result language

    angličtina

  • Original language name

    Time-Resolved Femtosecond Stimulated Raman Spectra and DFT Anharmonic Vibrational Analysis of an Electronically Excited Rhenium Photosensitizer

  • Original language description

    Time-resolved femtosecond stimulated Raman spectra (FSRS) of a prototypical organometallic photosensitizer/photocatalyst ReCl(CO)3(2,2′-bipyridine) were measured in a broad spectral range ∼40–2000 (4000) cm–1 at time delays from 40 fs to 4 ns after 400 nm excitation of the lowest allowed electronic transition. Theoretical ground- and excited-state Raman spectra were obtained by anharmonic vibrational analysis using second-order vibrational perturbation theory on vibrations calculated by harmonic approximation at density functional theory-optimized structures. A good match with anharmonically calculated vibrational frequencies allowed for assigning experimental Raman features to particular vibrations. Observed frequency shifts upon excitation (ν(ReCl) and ν(CC inter-ring) vibrations upward, ν(CC, CN) and ν(Re–C) downward) are consistent with the bonding/antibonding characters of the highest occupied molecular orbital and the lowest unoccupied molecular orbital involved in excitation and support the delocalized formulation of the lowest triplet state as ReCl(CO)3 → bpy charge transfer. FSRS spectra show a mode-specific temporal evolution, providing insights into the intersystem crossing (ISC) mechanism and subsequent relaxation. Most of the Raman features are present at ∼40 fs and exhibit small shifts and intensity changes with time. The 1450–1600 cm–1 group of bands due to CC, CN, and CC(inter-ring) stretching vibrations undergoes extensive restructuring between 40 and ∼150 fs, followed by frequency upshifts and a biexponential (0.38, 21 ps) area growth, indicating progressing charge separation in the course of the formation and relaxation of the lowest triplet state. Early (40–150 fs) restructuring was also observed in the low-frequency range for ν(Re–Cl) and δ(Re–C–O) vibrations that are presumably activated by ISC. FSRS experimental innovations employed to measure low- and high-energy Raman features simultaneously are described and discussed in detail.

  • Czech name

  • Czech description

Classification

  • Type

    J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database

  • CEP classification

  • OECD FORD branch

    10403 - Physical chemistry

Result continuities

  • Project

    Result was created during the realization of more than one project. More information in the Projects tab.

  • Continuities

    I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Others

  • Publication year

    2020

  • Confidentiality

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Data specific for result type

  • Name of the periodical

    Journal of Physical Chemistry A

  • ISSN

    1089-5639

  • e-ISSN

  • Volume of the periodical

    124

  • Issue of the periodical within the volume

    7

  • Country of publishing house

    US - UNITED STATES

  • Number of pages

    13

  • Pages from-to

    1253-1265

  • UT code for WoS article

    000515216300005

  • EID of the result in the Scopus database

    2-s2.0-85080845957