Molecular Structure and Bonding of Copper Cluster Monocarbonyls Cu_nCO (n = 1−9)

Abstract

In this work we analyze CO binding on small neutral copper clusters, Cun (n = 1-9). Molecular structures and reactivity descriptors of copper clusters are computed and discussed. The results show that the condensed Fukui functions and the frontier molecular orbital theory are useful tools to predict the selectivity of CO adsorption on these small clusters. To get further insight into the CO binding to copper clusters, an energy decomposition analysis of the CO binding energy is performed. The Cs symmetry of the formed CunCO clusters (n = 1-8) allows the separation between the orbital interaction terms corresponding to donation and back-donation. It is found that, energetically, the donation is twice as important as back-donation.

Modeling the structure‐property relationships of nanoneedles: A journey toward nanomedicine

“…38,39 The calculated values of the HOMO-LUMO energy gap (E HOMO-LUMO ), chemical potential (l), chemical hardness (g), and Parr electrophilicity (x) for C4, C6, and C8 CNNs have been collected in Table S1, for the different number of layers (N layers ). The E HOMO-LUMO gap decreases when increasing the number of layers.…”

A test of empirical correction to site preference: DFT calculations for CO adsorption on Co(0001) surface

“…There are much discussion on CO site preference on transition metals [8][9][10][11][12][13], especially when potential density functional theory-generalized gradient approximation (DFT-GGA) calculations predict CO favoring higher coordination adsorption sites in contradict with onefold atop site in experiments for such a few notorious cases as CO adsorption on Pd(1 1 1), Rh(1 1 1) and Cu(1 1 1) surfaces [1][2][3][4]. Calculations for CO adsorption on copper cluster by Cao et al show that the favored adsorption sites are dominated by the local orientation of relevant frontier orbitals and the distribution of overall electrostatic potential [10].…”

Density functional theory study of surface catalysis and adsorption on several elements in Group I-B and VIII

“…However, E ad1 values decrease to -1.01 and -1.03 eV/atom when l = 6 and 7. In general, the binding strength, or −E ad , is inversely proportional to its corresponding d value between the adsorbate and the substrate [226]. This is our case as shown in Table 4 where the trend of d 1C−Cu ∝ E ad1 .…”

“…11(b), from which it is discernable that β is identical to α, except the spin direction. This consists of the conditions of the HOMO (highest occupied molecular orbitals) and LUMO (lowest unoccupied molecular orbitals) orbitals for CO on small Cu clusters [226]. Comparing Fig.…”