First Principles Study of Polyatomic Clusters of AlN, GaN, and InN. 1. Structure, Stability, Vibrations, and Ionization

Abstract

In this paper we study the chemical bonding of the small (monomer, triatomic, and dimer) neutral clusters of AlN, GaN, and InN presented earlier in paper 1. It includes the analysis of the topology of the electron density and its Laplacian, together with relevant atomic properties, in light of the theory of atoms in molecules. The most prominent feature of the bonding here, the existence of strong N-N bonds, is seen to diminish with an increase in the number of metal atoms and the degree of ionicity. The Al-N bond shows a large transfer of charge, but also a significant deformation of the Al electron shells, so it can be understood as a highly polar shared interaction. On the other hand, Ga-N and In-N bonds are nonshared interactions, with smaller charge transfers and polarizations. In all cases, the existence of a N-N bond weakens the metalnitrogen bond. The bonding picture that emerges depends only on the reliability of the electron densities, and it is consistent with the conclusions of our previous work in paper 1.

Density Functional Calculations of Small Anionic Clusters of Group III Nitrides

“…2 Representing a link between the isolated molecular world and the solid state, the study of these clusters with different sizes has drawn increasing attention during the last few years; this attention was mainly focused on Al x N y . [3][4][5][6][7][8][9][10][11][12] A few studies were also carried out on Ga x N y and In x N y . [8][9][10][11]13 Recent experimental studies on gaseous AlN using infrared spectroscopy and the Knudsen cell mass showed the existence of a large diversity of neutral and charged species.…”

“…[3][4][5][6][7][8][9][10][11][12] A few studies were also carried out on Ga x N y and In x N y . [8][9][10][11]13 Recent experimental studies on gaseous AlN using infrared spectroscopy and the Knudsen cell mass showed the existence of a large diversity of neutral and charged species. 7,14,15 In addition, photoelectron spectroscopy experiments [16][17][18][19] and their theoretical analysis [20][21][22] were reported for Al x P y , Ga x P y , and In x P y .…”

“…We begin with the configurations of neutral group III nitride monomers, dimers, and trimers, which were obtained 8,9 using the DMol program. 23 This code employs double-numerical basis sets with polarization functions (DNP).…”

Surface bonding effects in compound semiconductor nanoparticles: II

“…GaAs clusters have been modeled by various groups including Chelikowsky and coworkers (15,16) and others (17)(18)(19)(20)(21)(22)(23)(24)(25). GaN clusters have also been studied by Pandey and coworkers (26)(27)(28) as well as others (29)(30)(31)(32). AlP has also been studied by a number of investigators (33)(34)(35)(36)(37).…”

Possible Pathways of CVD Processes Leading to III–V Semiconductors via a Two‐Dimensional Growth

“…Numerous derivatives of these oligomers (in which the H atoms are replaced by organic groups) were synthesised and structurally characterised with the help of X-ray diffraction. [7] Quantumchemical calculations on the reaction energies and structures of these oligomers in the light of possible CVD processes have especially been carried out by Thimoshkin et al [8][9][10] [11,12] Thus it is unlikely that solid AlN or GaN is formed via these molecules. In addition, the formal dimers Al 2 N 2 and Ga 2 N 2 were calculated to be essentially weak complexes of the metal atoms or dimers to dinitrogen.…”