Prediction of electronically nonadiabatic decomposition mechanisms of isolated gas phase nitrogen-rich energetic salt: Guanidium-triazolate

Ghosh, Jayanta and Bhattacharya, Atanu (2016) Prediction of electronically nonadiabatic decomposition mechanisms of isolated gas phase nitrogen-rich energetic salt: Guanidium-triazolate. In: CHEMICAL PHYSICS, 464 . pp. 26-39.

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Abstract

Electronically nonadiabatic decomposition pathways of guanidium triazolate are explored theoretically. Nonadiabatically coupled potential energy surfaces are explored at the complete active space self-consistent field (CASSCF) level of theory. For better estimation of energies complete active space second order perturbation theories (CASPT2 and CASMP2) are also employed. Density functional theory (DFT) with B3LYP functional and MP2 level of theory are used to explore subsequent ground state decomposition pathways. In comparison with all possible stable decomposition products (such as, N-2, NH3, HNC, HCN, NH2CN and CH3NC), only NH3 (with NH2CN) and N-2 are predicted to be energetically most accessible initial decomposition products. Furthermore, different conical intersections between the S-1 and S-0 surfaces, which are computed at the CASSCF(14,10)/6-31G(d) level of theory, are found to play an essential role in the excited state deactivation process of guanidium triazolate. This is the first report on the electronically nonadiabatic decomposition mechanisms of isolated guanidium triazolate salt. (C) 2015 Elsevier B.V. All rights reserved.

Item Type:	Journal Article
Publication:	CHEMICAL PHYSICS
Publisher:	ELSEVIER SCIENCE BV
Additional Information:	Copy right for this article belongs to the ELSEVIER SCIENCE BV, PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS
Keywords:	Electronically nonadiabatic decomposition; Computational chemistry; Energetic salts; Conical intersections; Electronically excited states; CASSCF, CASPT2, CASMP2 calculations
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	28 Jan 2016 05:47
Last Modified:	28 Jan 2016 05:47
URI:	http://eprints.iisc.ac.in/id/eprint/53169

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