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Electronic properties of mixed metal rod-like group 13 nitride oligomers [RMNH]10 and [R3(RMNH)9H3] (M = Al, Ga, In; R = CH3)

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Abstract

Structural and electronic properties of the rod-like oligomers formed by stacking of three [RMNH]3 rings and have been theoretically investigated using DFT/TDDFT methods. Two types of oligomers have been considered: closed ones (terminated by RM and NH units) and open ones (terminated by three methyl groups and three hydrogen atoms). It is shown that terminal groups have significant influence on the electronic properties of oligomers due to the highly edge-localized nature of band gap states and huge difference in dipole moments. Ground state DFT calculations reveal that compared to closed oligomers, a profound reduction of energy gaps (by 1.6, 1.3 and 0.8 eV for M = Al, Ga, and In, respectively) is observed for open oligomers. Substitution of Ga atoms by Al results in moderate increase of energy gaps (up to 0.5 eV). Effect of substitution Ga atoms by In depends on the position of the substituted atoms. Excited states follow the same tendencies observed for the energy gaps.

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Acknowledgments

This work was supported by SPbSU Grants 12.38.255.2014 and 12.50.1563.2013. Research was carried out using computational resources provided by Resource Center “Computer Center of SPbU”. We thank Alexandra Oranskaya for preliminary computations.

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Authors and Affiliations

  1. Inorganic Chemistry Group, Institute of Chemistry, St. Petersburg State University, University Pr. 26, Old Peterhof, St. Petersburg, 198504, Russia

    Anna V. Pomogaeva & Alexey Y. Timoshkin

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  1. Anna V. Pomogaeva
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  2. Alexey Y. Timoshkin
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Correspondence to Anna V. Pomogaeva.

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Pomogaeva, A.V., Timoshkin, A.Y. Electronic properties of mixed metal rod-like group 13 nitride oligomers [RMNH]10 and [R3(RMNH)9H3] (M = Al, Ga, In; R = CH3). Theor Chem Acc 133, 1572 (2014). https://doi.org/10.1007/s00214-014-1572-8

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