Crepin, Claudine and Shafizadeh, Niloufar and Chin, W. and Galaup, Jean-Pierre and McCaffrey, John G. and Arabei, Serguei (2010) Unveiled optical properties of tetrapyrollic pigments in cryogenic environments. Low Temperature Physics, 36 (5). pp. 451-457. ISSN 1063-777X

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Abstract

An unexpected phenomenon was revealed in the laser induced fluorescence spectra of free-base (H2Pc) and zinc (ZnPc) phthalocyanines trapped in rare gas and nitrogen matrices under a moderate increase in the laser intensity. In all matrices the intensity of an emission band near 755 nm increased drastically when pumping the S1 ← S0 transition. This observation was assigned to stimulated emission in a four-level scheme involving a vibronic transition from the lowest electronic state to a vibrational level of the ground state. In the present work, we expose new similar results obtained with porphyrin molecules, i.e. tetra-benzoporphin (TBP). With free-base H2TBP, stimulated emission was observed in Ar or N2 matrices, but not in Xe matrices. A possible reason could be a fast inter-system crossing rate due to the heavy atom effect induced by Xe. We also report the observation of persistent burnt spectral holes, although the low efficiency of this process is not competitive with stimulated emission and no decrease of the stimulated emission with time was observed. With ZnTBP, no stimulated emission could be recorded; however the appearance of rather strong phosphorescence was noticed. Similar studies focusing on the stimulated emission phenomenon is that they should allow new insights into site effects and site selectivity. PACS: 33.50.-j Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion); 33.80.-b Photon interactions with molecules; 78.47.-p Spectroscopy of solid state dynamics; 78.60.Lc Optically stimulated luminescence.

Item Type:	Article
Keywords:	Unveiled optical properties; tetrapyrollic pigments; cryogenic environments;
Academic Unit:	Faculty of Science and Engineering > Chemistry
Item ID:	7847
Identification Number:	https://doi.org/10.1063/1.3432263
Depositing User:	Dr. John McCaffrey
Date Deposited:	01 Feb 2017 17:38
Journal or Publication Title:	Low Temperature Physics
Publisher:	AIP Publishing
Refereed:	Yes
URI:	http://aip.scitation.org
Use Licence:	This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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