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Optical Materials Express

Optical Materials Express

  • Editor: David J. Hagan
  • Vol. 1, Iss. 2 — Jun. 1, 2011
  • pp: 293–304

Primary photo-events in a metastable photomerocyanine of spirooxazines

R. Sai Santosh Kumar, Larry Lüer, Dario Polli, Michele Garbugli, and Guglielmo Lanzani  »View Author Affiliations

Optical Materials Express, Vol. 1, Issue 2, pp. 293-304 (2011)

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We report on the ultrafast excited-state relaxation dynamics of the metastable photo-merocyanine (open-form) isomer of spiro-phenantroxazine, measured by pump and probe spectroscopy with sub-40-fs temporal resolution. We found that the photo-induced yield for ring-closure is negligible, and that the excited-state lifetime is only on the order of 300 fs. Relaxation leads to the non-adiabatic formation of a hot ground state (HGS). In this state, a coherent oscillation with 45 cm−1 frequency is present, showing strong anharmonicity. We attribute it to the motion (torsion/bending) of the molecular backbone attempting geometric relaxation to the close form. The strength of the coherent oscillation and the subsequent spectral relaxation in the HGS, together with the ultrashort lifetime, points to a crossing through a conical intersection (CI). We conclude that excited-states on the merocyanine form pass through a CI that is different from the one that would lead to ring-closure. We discuss design rules for the spiro-oxazine class, allowing for bidirectional switching avoiding this parasitic CI.

© 2011 OSA

OCIS Codes
(160.2900) Materials : Optical storage materials
(160.4890) Materials : Organic materials
(320.7150) Ultrafast optics : Ultrafast spectroscopy

ToC Category:
Organics and Polymers

Original Manuscript: April 12, 2011
Revised Manuscript: May 20, 2011
Manuscript Accepted: May 23, 2011
Published: May 27, 2011

R. Sai Santosh Kumar, Larry Lüer, Dario Polli, Michele Garbugli, and Guglielmo Lanzani, "Primary photo-events in a metastable photomerocyanine of spirooxazines," Opt. Mater. Express 1, 293-304 (2011)

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