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
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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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
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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