We report on the first observation of reverse saturable absorption by ferrocene (Fc) in toluene using nanosecond pulses at 532 nm. Pump and probe experiments in the visible spectral region show the existence of an excited triplet state with an intersystem crossing quantum yield S-1 -> T-1 of 0.085 and a molar extinction coefficient epsilon(T)(Fc) of 5650 L mol(-1) cm(-1) at 700 nm. The full understanding of the nonlinear optical behavior of Fc cannot be obtained, however, with a model that includes only the one-photon absorption from T-1, but it is mandatory to consider also a simultaneous two-photon absorption from an excited singlet state of Fc (two-photon absorption cross section: 2.4 x 10(-41) cm(4) s ph(-1) mol(-1)). The optical spectrum of the ground and triplet state of Fc are calculated within a TD-DFT approach considering several functionals (PBE, BLYP, LDA, OPBE) for the optimization of molecular geometry.
Nonlinear Absorption Properties and Excited State Dynamics of Ferrocene / Stefano, Scuppa; Laura, Orian; Dini, Danilo; Saverio, Santi; Moreno, Meneghetti. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - 113:33(2009), pp. 9286-9294. [10.1021/jp9047192]
Nonlinear Absorption Properties and Excited State Dynamics of Ferrocene
DINI, DANILO;
2009
Abstract
We report on the first observation of reverse saturable absorption by ferrocene (Fc) in toluene using nanosecond pulses at 532 nm. Pump and probe experiments in the visible spectral region show the existence of an excited triplet state with an intersystem crossing quantum yield S-1 -> T-1 of 0.085 and a molar extinction coefficient epsilon(T)(Fc) of 5650 L mol(-1) cm(-1) at 700 nm. The full understanding of the nonlinear optical behavior of Fc cannot be obtained, however, with a model that includes only the one-photon absorption from T-1, but it is mandatory to consider also a simultaneous two-photon absorption from an excited singlet state of Fc (two-photon absorption cross section: 2.4 x 10(-41) cm(4) s ph(-1) mol(-1)). The optical spectrum of the ground and triplet state of Fc are calculated within a TD-DFT approach considering several functionals (PBE, BLYP, LDA, OPBE) for the optimization of molecular geometry.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
