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Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy
[Image: see text] The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2014
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4136751/ https://www.ncbi.nlm.nih.gov/pubmed/24841906 http://dx.doi.org/10.1021/ja503541v |
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author | Balakrishnan, Gurusamy Soldatova, Alexandra V. Reid, Philip J. Spiro, Thomas G. |
author_facet | Balakrishnan, Gurusamy Soldatova, Alexandra V. Reid, Philip J. Spiro, Thomas G. |
author_sort | Balakrishnan, Gurusamy |
collection | PubMed |
description | [Image: see text] The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study the photoexcitation dynamics of nickel(II) phthalocyanine with eight butoxy substituents, NiPc(OBu)(8). NiPc(OBu)(8) is reported to have a relatively long-lived ligand-to-metal charge-transfer (LMCT) state, an essential characteristic for efficient electron transfer in photocatalysis. Following photoexcitation, vibrational transitions in the FRIKES spectra, assignable to phthalocyanine ring modes, evolve on the femtosecond to picosecond time scales. Correlation of ring core size with the frequency of the ν(10) (asymmetric C–N stretching) mode confirms the identity of the LMCT state, which has a ∼500 ps lifetime, as well as that of a precursor d-d excited state. An even earlier (∼0.2 ps) transient is observed and tentatively assigned to a higher-lying Jahn–Teller-active LMCT state. This study illustrates the power of FRIKES spectroscopy in elucidating ultrafast molecular dynamics. |
format | Online Article Text |
id | pubmed-4136751 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2014 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-41367512014-08-18 Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy Balakrishnan, Gurusamy Soldatova, Alexandra V. Reid, Philip J. Spiro, Thomas G. J Am Chem Soc [Image: see text] The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study the photoexcitation dynamics of nickel(II) phthalocyanine with eight butoxy substituents, NiPc(OBu)(8). NiPc(OBu)(8) is reported to have a relatively long-lived ligand-to-metal charge-transfer (LMCT) state, an essential characteristic for efficient electron transfer in photocatalysis. Following photoexcitation, vibrational transitions in the FRIKES spectra, assignable to phthalocyanine ring modes, evolve on the femtosecond to picosecond time scales. Correlation of ring core size with the frequency of the ν(10) (asymmetric C–N stretching) mode confirms the identity of the LMCT state, which has a ∼500 ps lifetime, as well as that of a precursor d-d excited state. An even earlier (∼0.2 ps) transient is observed and tentatively assigned to a higher-lying Jahn–Teller-active LMCT state. This study illustrates the power of FRIKES spectroscopy in elucidating ultrafast molecular dynamics. American Chemical Society 2014-05-19 2014-06-18 /pmc/articles/PMC4136751/ /pubmed/24841906 http://dx.doi.org/10.1021/ja503541v Text en Copyright © 2014 American Chemical Society Terms of Use (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) |
spellingShingle | Balakrishnan, Gurusamy Soldatova, Alexandra V. Reid, Philip J. Spiro, Thomas G. Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy |
title | Ultrafast
Charge Transfer in Nickel Phthalocyanine
Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy |
title_full | Ultrafast
Charge Transfer in Nickel Phthalocyanine
Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy |
title_fullStr | Ultrafast
Charge Transfer in Nickel Phthalocyanine
Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy |
title_full_unstemmed | Ultrafast
Charge Transfer in Nickel Phthalocyanine
Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy |
title_short | Ultrafast
Charge Transfer in Nickel Phthalocyanine
Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy |
title_sort | ultrafast
charge transfer in nickel phthalocyanine
probed by femtosecond raman-induced kerr effect spectroscopy |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4136751/ https://www.ncbi.nlm.nih.gov/pubmed/24841906 http://dx.doi.org/10.1021/ja503541v |
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