Internal conversion (IC) is a common radiationless transition in polyatomic molecules. Theory predicts that molecular vibrations assist IC between excited states, and ultrafast experiments can provide insight into their structure-function relationship. Here we elucidate the dynamics of the vibrational modes driving the IC process within the Q band of a functionalized porphyrin molecule. Through a combination of ultrafast multidimensional spectroscopies and theoretical modeling, we observe a 60 fs Q(y)-Q(x) IC and demonstrate that it is driven by the interplay among multiple high-frequency modes. Notably, we identify 1510 cm(-1) as the leading tuning mode that brings the porphyrin to an optimal geometry for energy surface crossing. By employing coherent wave packet analysis, we highlight a set of short-lived vibrations (1200-1400 cm(-1)), promoting the IC within approximate to 60 fs. Furthermore, we identify one coupling mode (1350 cm(-1)) that is responsible for vibronic mixing within the Q states. Our findings indicate that porphyrin-core functionalization modulates IC effectively, offering new opportunities in photocatalysis and optoelectronics.
Vibronic Coupling Drives the Ultrafast Internal Conversion in a Functionalized Free-Base Porphyrin / Petropoulos, V.; Rukin, P. S.; Quintela, F.; Russo, M.; Moretti, L.; Moore, A.; Moore, T.; Gust, D.; Prezzi, D.; Scholes, G. D.; Molinari, E.; Cerullo, G.; Troiani, F.; Rozzi, C. A.; Maiuri, M.. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 15:16(2024), pp. 4461-4467. [10.1021/acs.jpclett.4c00372]
Vibronic Coupling Drives the Ultrafast Internal Conversion in a Functionalized Free-Base Porphyrin
Prezzi D.;Molinari E.;Troiani F.
;Rozzi C. A.
;
2024
Abstract
Internal conversion (IC) is a common radiationless transition in polyatomic molecules. Theory predicts that molecular vibrations assist IC between excited states, and ultrafast experiments can provide insight into their structure-function relationship. Here we elucidate the dynamics of the vibrational modes driving the IC process within the Q band of a functionalized porphyrin molecule. Through a combination of ultrafast multidimensional spectroscopies and theoretical modeling, we observe a 60 fs Q(y)-Q(x) IC and demonstrate that it is driven by the interplay among multiple high-frequency modes. Notably, we identify 1510 cm(-1) as the leading tuning mode that brings the porphyrin to an optimal geometry for energy surface crossing. By employing coherent wave packet analysis, we highlight a set of short-lived vibrations (1200-1400 cm(-1)), promoting the IC within approximate to 60 fs. Furthermore, we identify one coupling mode (1350 cm(-1)) that is responsible for vibronic mixing within the Q states. Our findings indicate that porphyrin-core functionalization modulates IC effectively, offering new opportunities in photocatalysis and optoelectronics.File | Dimensione | Formato | |
---|---|---|---|
petropoulos-et-al-2024-vibronic-coupling-drives-the-ultrafast-internal-conversion-in-a-functionalized-free-base.pdf
Accesso riservato
Tipologia:
AO - Versione originale dell'autore proposta per la pubblicazione
Dimensione
4.67 MB
Formato
Adobe PDF
|
4.67 MB | Adobe PDF | Visualizza/Apri Richiedi una copia |
Pubblicazioni consigliate
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris