Molecules 2013, 18(11), 14148-14160; doi:10.3390/molecules181114148
Concept Paper

Topography of Photochemical Initiation in Molecular Materials

1 Department of Physical Chemistry, Kemerovo State University, Kemerovo 650043, Russia 2 Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742, USA
* Author to whom correspondence should be addressed.
Received: 14 October 2013; in revised form: 8 November 2013 / Accepted: 12 November 2013 / Published: 15 November 2013
(This article belongs to the Special Issue Surface Chemistry)
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Abstract: We propose a fluctuation model of the photochemical initiation of an explosive chain reaction in energetic materials. In accordance with the developed model, density fluctuations of photo-excited molecules serve as reaction nucleation sites due to the stochastic character of interactions between photons and energetic molecules. A further development of the reaction is determined by a competition of two processes. The first process is growth in size of the isolated reaction cell, leading to a micro-explosion and release of the material from the cell towards the sample surface. The second process is the overlap of reaction cells due to an increase in their size, leading to the formation of a continuous reaction zone and culminating in a macro-explosion, i.e., explosion of the entire area, covering a large part of the volume of the sample. Within the proposed analytical model, we derived expressions of the explosion probability and the duration of the induction period as a function of the initiation energy (exposure). An experimental verification of the model was performed by exploring the initiation of pentaerythritol tetranitrate (PETN) with the first harmonic of YAG: Nd laser excitation (1,064 nm, 10 ns), which has confirmed the adequacy of the model. This validation allowed us to make a few quantitative assessments and predictions. For example, there must be a few dozen optically excited molecules produced by the initial fluctuations for the explosive decomposition reaction to occur and the life-time of an isolated cell before the micro-explosion must be of the order of microseconds.
Keywords: molecular energetic materials; high explosive decomposition; laser excitation; PETN; excitonic mechanism of initiation

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MDPI and ACS Style

Aluker, E.D.; Krechetov, A.G.; Mitrofanov, A.Y.; Zverev, A.S.; Kuklja, M.M. Topography of Photochemical Initiation in Molecular Materials. Molecules 2013, 18, 14148-14160.

AMA Style

Aluker ED, Krechetov AG, Mitrofanov AY, Zverev AS, Kuklja MM. Topography of Photochemical Initiation in Molecular Materials. Molecules. 2013; 18(11):14148-14160.

Chicago/Turabian Style

Aluker, Edward D.; Krechetov, Alexander G.; Mitrofanov, Anatoly Y.; Zverev, Anton S.; Kuklja, Maija M. 2013. "Topography of Photochemical Initiation in Molecular Materials." Molecules 18, no. 11: 14148-14160.

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