Hybrid hard- and soft-modelling applied to analyze ultrafast processes by femtosecond transient absorption spectroscopy: Study of the photochromism of salicylidene anilines

C. Ruckebusch, M. Sliwa, J. Réhault, P. Naumov, J. P. Huvenne, G. Buntinx

Research output: Contribution to journalArticle

Abstract

Multivariate curve resolution-alternating least squares (MCR-ALS) of multi-experiment data analysis was successfully applied to elucidate the photodynamics of the N-(3-methylsalicylidene)-3-methylaniline by analyzing UV-vis femtosecond transient absorption spectra. The two-way data obtained present some specific difficulties linked to the nature of the transient spectra collected and to the overlapping of the photodynamics of the solvent and other contributions at short time scale (below 1 ps). Advantage was taken from the flexibility of the hybrid hard-soft multivariate curve resolution (HS-MCR) approach to consider a non-absorbing contribution in the kinetic model and to provide a functional description of the solvent in soft-modelling. The results obtained confirm the existence of an intermediate excited state in the process, which is created just after the ESIPT. It was observed that this intermediate relaxes in a few hundreds of femtosecond to the S1 fluorescent cis-keto excited state and a decay time constant of 219 fs was found. These results confirm other femtosecond time-resolved fluorescence studies on salicylidene aniline molecules. Previous hypothesis on the formation of the trans-keto photoproduct from the S1 fluorescent cis-keto state (time constant 14 ps) is also confirmed.

Original languageEnglish (US)
Pages (from-to)228-234
Number of pages7
JournalAnalytica Chimica Acta
Volume642
Issue number1-2
DOIs
StatePublished - May 29 2009

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Keywords

  • Femtosecond spectroscopy
  • Kinetic modelling
  • MCR-ALS
  • Multivariate curve resolution
  • Salicylidene aniline

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry
  • Environmental Chemistry
  • Spectroscopy

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