Antibonding

Fig. XVIII-16. A four-electron two-orbital interaction that a) has no net bonding in the free molecule but can be bonding to a metal surface if (b) the Fermi level is below the antibonding level. In the lower part of the figure, a zero-electron two-orbital situation (c) has no bonding but there can be bonding to a metal surface as in (d) if the Fermi level is above the bonding level. (From Ref. 160.)...

Figure Bl.6.11 Electron transmission spectrum of 1,3-cyclohexadiene presented as the derivative of transmitted electron current as a fiinction of the incident electron energy [17]. The prominent resonances correspond to electron capture into the two unoccupied, antibonding a -orbitals. The negative ion state is sufficiently long lived that discrete vibronic components can be resolved.

Chemical reactions of aimnonia with the silicon surface have also been clearly observed using STS [21], where the disappearance of the it and it states characteristic of the clean surface coincides with the fomiation of Si-H antibonding states corresponding to the dissociation of the ammonia on the Si surface. 

Figure 7-18. Schematic representation of the LCAO scheme in a, T-only calculation for ethylene, The AOs

The triplet excited state of H2 is obtained by promoting an electron to a higher-energy molecular orbital. This higher-energy (antibonding) orbital is written and can be considered to arise from two Is orbitals as follows ... 

I he results of their calculations were summarised in two rules. The first rule states that at least one isomer C with a properly closed p shell (i.e. bonding HOMO, antibonding I. U.MO) exists for all n = 60 - - 6k (k = 0,2,3,..., but not 1). Thus Qg, C72, Cyg, etc., are in lhi-< group. The second rule is for carbon cylinders and states that a closed-shell structure is lound for n = 2p(7 - - 3fc) (for all k). C70 is the parent of this family. The calculations Were extended to cover different types of structure and fullerenes doped with metals. 

The antibonding orbital remains empty for the free radical and both of the ions. 

What is the energy separation E2 — E of the bonding and antibonding orbitals in ethylene, assuming that the overlap integral S is 0.27 ... 

Valence Atomic Orbitals on Neighboring Atoms Combine to Form Bonding, Non-Bonding and Antibonding Molecular Orbitals... 

When aos are eombined to form mos, eore, bonding, nonbonding, antibonding, and Rydberg moleeular orbitals ean result. The mos (j) are usually expressed in terms of the eonstituent atomie orbitals Xa iii the linear-eombination-of-atomie-orbital-moleeular-orbital (LCAO-MO) manner ... 

Here an is used to denote the non-bonding a-type orbitals and a, a, n, and 7i are used to denote bonding and antibonding a- and 7i-type orbitals. 

The O atom uses one of its sp or sp hybrids to form the CO a bond and antibond. When sp hybrids are used in conceptualizing the bonding, the other sp hybrid forms a lone pair orbital directed away from the CO bond axis one of the atomic p orbitals is involved in the CO n and 71 orbitals, while the other forms an in-plane non-bonding orbital. Alternatively, when sp hybrids are used, the two sp hybrids that do not interact with the C-atom sp2 orbital form the two non-bonding orbitals. Hence, the final picture of bonding, non-bonding, and antibonding orbitals does not depend on which hybrids one uses as intermediates. 

For example, the three NH bonding and three NH antibonding orbitals in NH3, when symmetry adapted within the C3V point group, cluster into ai and e mos as shown in the Figure below. The N-atom localized non-bonding lone pair orbital and the N-atom Is core orbital also belong to ai symmetry. 

In a second example, the three CH bonds, three CH antibonds, CO bond and antibond, and three 0-atom non-bonding orbitals of the methoxy radical H3C-O also cluster into ai and e orbitals as shown below. In these cases, point group symmetry allows one to identify degeneracies that may not have been apparent from the structure of the orbital interactions alone. 

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