Abstract
In this work, the structures of cationic SinNb(+) (n = 4-12) clusters are determined using the combination of infrared multiple photon dissociation (IR-MPD) and density functional theory (DFT) calculations. The experimental IR-MPD spectra of the argon complexes of SinNb(+) are assigned by comparison to the calculated IR spectra of low-energy structures of SinNb(+) that are identified using the stochastic 'random kick' algorithm in conjunction with the BP86 GGA functional. It is found that the Nb dopant tends to bind in an apex position of the Sin framework for n = 4-9 and in surface positions with high coordination numbers for n = 10-12. For the larger doped clusters, it is suggested that multiple isomers coexist and contribute to the experimental spectra. The structural evolution of SinNb(+) clusters is similar to V-doped silicon clusters (J. Am. Chem. Soc., 2010, 132, 15589-15602), except for the largest size investigated (n = 12), since V takes an endohedral position in Si12V(+). The interaction with a Nb atom, with its partially unfilled 4d orbitals leads to a significant stability enhancement of the Sin framework as reflected, e.g. by high binding energies and large HOMO-LUMO gaps.
Highlights
In this work, the structures of cationic SinNb+ (n = 4–12) clusters are determined using the combination of infrared multiple photon dissociation (IR-MPD) and density functional theory (DFT) calculations
The results show that Ar does not affect the energetic ordering for most low-energy isomers, with the exception of Si11Nb+ and has only a minor effect on the vibrational frequencies and infrared intensities (see Fig. S1(a–d) of the Electronic supplementary information (ESI)†)
The identified low-lying structures for each cluster size are labeled as iso[1], iso[2], iso[3], etc., along with increasing relative energies obtained at the BP86/def-SVP level of theory
Summary
It has been found that silicon clusters can be stabilized by doping with transition metal (TM) atoms,[14,15,16] and a great number of studies, both experimentally[17,18,19,20,21,22,23,24,25,26,27,28,29] and theoretically,[30,31,32,33,34,35,36] have explored the structures and electronic properties of TM-doped silicon clusters for their potential use in silicon-based nanomaterials. We report on a combined experimental and theoretical study investigating the structures, stabilities, and electronic properties of cationic Nb-doped silicon clusters, SinNb+ (n = 4–12), applying infrared multiple photon dissociation (IR-MPD) spectroscopy to the cationic cluster– Ar complexes together with density functional theory (DFT) calculations
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