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Local structure and triplet energy migration inp-dichlorobenzene-p-dibromobenzene solid solutions

 

作者: Veronica Vaida,   StevenD. Colson,  

 

期刊: Molecular Physics  (Taylor Available online 1978)
卷期: Volume 35, issue 4  

页码: 965-974

 

ISSN:0026-8976

 

年代: 1978

 

DOI:10.1080/00268977800100711

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

Studies of the first triplet absorption and emission spectra ofp-dichlorobenzene-p-dibromobenzene (DCB-DBB) mixed crystals agree generally with the data, indicating that this system forms solid solutions. However, the spectral properties are found to be very different from that of isotopically mixed crystals of comparable concentrations. The singlet-triplet absorption spectra of the DCB-DBB mixtures are generally broad and not amenable to detailed analysis indicating significant site dependent perturbations of the DCB and DBB triplet energies. Energy migration enhances emission from the lower energy sites and in consequence a red shift in the position of the emission (0,0) is observed, which is a maximum at equimolar concentrations. The emission bands are generally much broader than found for isotopically mixed crystals, indicating that the many types of sites in the DCB-DBB system remained uncoupled. This is a direct consequence of exciton trapping by inhomogeneous energy broadening caused by the site energy disorder being greater than the triplet exciton band width. Long-range triplet energy migration is not observed at DCB concentrations less than 99 per cent. This high limit is only expected for near one-dimension energy migration topologies. New structure observed at low DCB concentrations is tentatively interpreted as being due to the formation of DCBn-mers. The observed splittings indicate that the gas-to-crystal shift of the DCBT1state increases (becomes more negative) by 11 cm-1when a neighbouring DBB molecule is replaced by DCB.

 

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