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Flat-Structural Motives in Small Alumino-Carbon Clusters Cnalm (N ) 2-3, M ) 2-8)

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Flat-Structural Motives in Small Alumino-Carbon Clusters Cnalm (N ) 2-3, M ) 2-8) 4660 J. Phys. Chem. A 2008, 112, 4660–4668 Flat-structural Motives in Small Alumino-Carbon Clusters CnAlm (n ) 2-3, m ) 2-8) Fedor Y. Naumkin* Faculty of Science, UniVersity of Ontario Institute of Technology, Oshawa, ON L1H 7K4, Canada ReceiVed: NoVember 27, 2007; ReVised Manuscript ReceiVed: February 17, 2008 Small clusters consisting of a carbon diatom or triatom and several aluminum atoms are investigated ab initio, at an MP2 level of theory. The mainly ionic character of C-Al bonding predominantly leads to structures different from corresponding hydrocarbons (also if starting from analogous initial geometries), while still producing closed-shell ground states. It is found that in many cases stable geometries correspond to flat CAl3 units. These include unique metal-framed dicarbon and tricarbon all-flat species with unusual planar tetra- coordination. Another frequent feature is a hyper-coordination of carbon atoms, supported by their high negative charges and critically examined via atom-in-molecule calculations. Also characterized are anionic states, electronic excitation and ionization, electron attachment and detachment, and charge distributions. Introduction Computational Tools and Methods. Calculations have been carried out at the MP2 level with the aug-cc-pvtz and cc-pvtz Metal clusters have specific geometries and physical-chemical basis sets11 for carbon and aluminum, respectively, as imple- properties determined by their quantum sizes and large surface- mented in the NWChem ab initio package.12 Auxiliary calcula- to-volume ratio. These properties also depend on the cluster tions have been carried out at the DFT level with the PBE0 shape and composition and vary upon doping with other metal functional and the same basis sets. or nonmetal atoms. Doping with molecular species adds further At the MP2 level, the C and Al equilibrium internuclear multidimensionality to the cluster structure and property varia- 2 2 distances are calculated as R ) 1.25 and 2.45 Å, respectively, tions, which can be useful for practical applications such as e reproducing experimental data13 within 0.01 Å. The predicted catalysis, new (nanostructured) materials, or molecular devices. dissociation energy De ) 1.39 eV for Al2 fits well the This work focuses on molecules incorporated into metal clusters 13 up to being their cores, rather than adsorbed on their surfaces. experimental values 1.61 eV (listed in the NIST database ) and - R ) Recent examples of such systems include Si Au and Au BO 1.36 eV (as cited in ref 14). For CAl, values e 1.97 Å and 3 3 3 D ) complexes1,2 (also considered from the viewpoint of metal-carbon e 3.51 eV are calculated, favorably comparing with values - of 1.95 Å from experiments15 and 1.95 Å and 3.41 eV from versus hydrogen carbon bonding) and a gold-cage cluster with 16 3 CCSD(T) calculations. The electron affinity of C2 and ioniza- a molecular carbon core, C5Au12 (a structural analogue of C H ). In the present work, analogous smaller systems are tion potential of Al are predicted to be 3.26 and 5.81 eV, 5 12 respectively, which are in a nice agreement with experimental investigated, namely, diatomic and triatomic carbon molecules 13 with up to eight aluminum atoms attached. values of 3.27 and 5.99 eV. 4,5 Previous studies have dealt with C2Al and C2Al2 species. For each CnAlm system, all-atom optimization has been It was found that the latter, in its most stable isomer, resembles performed in a low symmetry (C1), and energy minima have Al-substituted acetylene, whereas the former is most stable in been verified by vibrational frequency calculations. Charge a T-shaped (or cyclic) geometry, thus without a hydrocarbon distributions have been characterized in terms of natural charges analogue. Apparent questions are whether larger similar systems, on atoms. Atom-in-molecule (AIM)17 calculations have been CnAlm, may also have hydrocarbon-like geometries and/or what employed to analyze critical points and electron densities. The different structures may be found. One such system is C2Al3, obtained geometries have been visualized using the ViewMol3D 6 18 found to resemble C2Al2 with the third aluminum attached on software, and the electron densities were plotted with the 19 the side (like in C2Al), thus having no hydrocarbon counterpart. Molekel software. - Related questions are whether CnAlm (n > 1, m > 1) other Because the dissociation energies decrease in the row C C, 7 - - than C2Al2 may have flat geometries, similar to CAl3 and (near- C Al, Al Al, in the present study the initial geometries of 6 flat) C2Al3 and/or may perhaps exhibit hyper-coordinated CnAlm have been limited to nondissociated dicarbon or tricarbon carbon atoms, by analogy to electronically similar carboranes, in contact with aluminum atoms. In particular, geometries 8 CnBm. In particular, CAl4 (i.e., Al-substituted methane) has analogous to those of hydrocarbon counterparts (with the same previously been found to have both flat and tetrahedral isomers, number of hydrogens), facilitating efficient C-Al bonding, have 9 - 10 ) the latter being more stable, and CAl4 is predicted to be flat. been employed. Only even numbers of Al atoms (beyond m These flat systems have unusual planar tetra-coordination of 1) have been chosen, sufficient to complement the system to a carbon. It is therefore interesting to check if such a feature may closed shell. The relative stabilization of the obtained singlet also be present in larger alumino-carbon clusters and also how states have been checked by comparing with the triplet states the extra charge influences shapes of their anions. The present of the systems. Although the present study is not aimed at an study is aimed to address the issues mentioned above. extensive search of various isomers of each CnAlm, the above cluster-construction logic is expected to lead to, at least, low- * E-mail: [email protected]. energy local minima. 10.1021/jp711230x CCC: $40.75 2008 American Chemical Society Published on Web 04/22/2008 Flat-structural Motives in Alumino-Carbon Clusters J. Phys. Chem. A, Vol. 112, No. 20, 2008 4661 - TABLE 1: Equilibrium Parameters (in eV and Å) of CnAlm and CnAlm Clusters a system symmetry/state De Re(C-C) Re(C-Al) Re(Al-Al) 2 c c c C2Al linear C∞V/ Σ 4.10 and 4.68 1.19, 1.25 1.98, 2.02 2 c c c T-shaped C2V/ A1 5.51 and 5.06 1.28, 1.29 1.90, 1.94 1 d d C2Al2 linear D∞h/ Σg 9.99 and 8.60 1.25, 1.25 1.97, 1.98 1 T-shaped C2V/ A1 7.75 and 6.36 1.28 1.91 2.79 - d d C2Al2 linear 7.3 1.26, 1.27 1.92, 1.94|1.93 2 T-shaped C2V/ B1 6.0 1.28 1.97 2.70 1 b C2Al4 flat D2h/ Ag 15.45 and 9.05 1.32 1.98, 2.13 3.33 1 b side-on Cs/ A′ 14.67 and 8.27 1.30 1.97, 2.10-2.17 2.46-3.04 - 2 b C2Al4 flat D2h/ B2g 14.06 1.36 1.91, 2.07 3.24 1 b C2Al6 end-on Cs/ A′ 22.84 and 9.18 1.41 1.93, 2.03-2.26 2.61-3.10 1 b side-on C2/ A 22.38 and 8.73 1.35 1.98, 2.11-2.32 2.55-2.88 - 2 b C2Al6 end-on Cs/ A′ 20.81 1.43 1.96, 2.04-2.58 2.54-2.95 2 b bipyramid D4h/ B1g 21.04 1.39 1.91, 2.17 2.91, 3.32 1 b C3Al4 C2V/ A1 14.84 and 8.45 1.32 1.94, 2.15, 2.28 2.94, 3.42 - 2 b C3Al4 C2V/ A1 1.31 1.93, 2.19-2.27 2.60, 2.91 1 b C3Al6 flat D2h/ Ag 20.59 and 6.94 1.33 1.99, 2.06, 2.53 2.76, 2.96 1 b C3-cycle C2/ A 20.67 and 7.01 1.42, 2 × 1.55 2.03-2.28 2.87-3.29 1 b C3Al8 convex C3 Cs/ A′ 27.24 1.35-1.36 2.00, 2.07-2.73 2.69-3.09 1 b concave C3 C2V/ A1 27.58 1.42 2.13, 2.19-2.40 2.63-2.75 a b c d CnAlm f Cn + mAl and f Cn + Alm. For Al on the sides of Cn. See reference 4, CCSD-T/6-311+G*. See reference 5, CCSD-T/ 6-311+G* | MP2/6-311+G*. TABLE 2: Vertical Electronic-perturbation Energies (in eV) could formally be associated with two C-Al interactions at 0.1 of CnAlm Clusters Å shorter distances, compensating for a weaker, 0.1 Å longer ) f system VIE VEA VE* (S 0 1) C-C bond (Table 1). This is in general accord with previous 4 C2Al2 linear 8.72 0.36 2.33 results (whose parameters are given in Table 1 as well), except T-shaped 8.20 1.60 1.27 for their assignment of the linear geometry as a saddle point at C2Al4 flat 8.22 1.73 1.77 the CCSD-T level. The appreciable lowest vibrational frequency side-on 7.71 1.51 1.67 of 480 cm-1 in the present MP2 calculations allows us to C2Al6 end-on 9.54 1.14 3.47 side-on 7.86 1.07 2.26 consider the linear isomer.
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