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When an atom such as boron (or some other group III element) replaces one silicon atom, the silicon is said to be a p-type (region) In this arrangement, the boron can bond to three silicon atoms in the crystal lattice; however, there is a hole left where the fourth bond used to be It follows that bonding electrons from the outer orbital of other Si atoms can move to ll this hole; in turn, this leaves a hole behind where the electrons came from in the crystal The net e ect is that the Si can sustain conduction as electrons move into holes in the system.

of carbenes in 7) Thus the con guration of S0 is F F F fHOMO-1 2 fHOMO 2 Excited singlet states are obtained by single (or multiple) electron excitations from the occupied MOs The rst (lowest energy) excited singlet state is usually that obtained from a HOMO-to-LUMO excitation and is designated S1 , with con guration F F F fHOMO-1 2 fHOMO 1 fLUMO 1 or, more descriptively, by the MOs involved in the transition (if the MOs are known), for example, 1 nO p States with doubly occupied MOs only must be singlet states Where ``open shells'' are involved, additional states must be considered from reversal of electron spin(s).

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If a p-type Si region is placed beside an n-type Si region, then a depletion layer forms where electrons and holes annihilate each other; also, electrons cannot ow between these two regions unless a suitable voltage is applied between them (stated in other words, the p n junction stops electrons from owing across the system) These observations can be used to construct a usable transistor, such as the metal oxide semiconductor eld e ect transistor (MOSFET), depicted diagrammatically in Figure 29 A MOSFET is a planar device of semiconducting material whose free-carrier concentration and, hence, its conductivity are controlled by the gate This transistor is a p-type silicon substrate with an insulator (oxide) and a metal strip (gate) on top It is comprised of two back-to-back p n junctions.

When two electrons have the same spin, the state is a triplet, designated T1 Y T2 Y F F F Y in order of increasing energy, or by a superscript in front of the state descriptor, for example, 3 nO p The spatial symmetry of the state is, in practice, determined by the cross product of the spatial symmetries of the SOMOs by the following rules: S S A S, A A A S, S A A A, A S A A The ``closed-shell'' states, like the ground state, are S with respect to every symmetry operation or transform as the totally symmetric irreducible representation of any point group The energies of the electronic states may be derived from simple Huckel consid erations (MO energy di erences) Triplet states are lower than the singlets with the same MO con guration.

Without a gate voltage applied, no current ows from the source n-type Si contact and the sink (drain) n-type Si contact When a voltage is applied to the gate, electrons are attracted to the gate and they form a thin layer in the proximity of the surface of the p-type Si It then follows.

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The separation of 3 nO p and 1 nO p is relatively small, whereas the separation of 3 pp and 1 pp is large Singlet states may be reached directly from the ground state by photoexcitation at the appropriate frequency The electron rearrangement associated with the excitation process is very rapid (about 10 15 s), and the nuclei do not have time to move to their new equilibrium positions The dynamics of the excitation process and the fate of excited electronic states are discussed in 15 Rules for Correlation of Electronic States When the electronic states of both the reactants and products have been determined and characterized, a correlation diagram may be constructed by connecting the states according to the following rules: 1 As with orbital correlation diagrams, states are correlated from the lowest to the highest 2.

Return Loss (dB)

Reactant states will only correlate with product states of the same spatial symmetry and spin multiplicity 3 Correlation lines de ne potential energy ``surfaces'' Surfaces are allowed to cross (intersect) if the states involved are di erent in spatial symmetry or spin multiplicity but may not cross if both characteristics are the same 4 Inspection of the orbital make-up of reactant and product states may imply intended correlations which would lead to state crossings If the states involved may not cross by rule 3, an avoided crossing occurs The intention to cross is often depicted by dashed lines Example: Carbene Addition to an Olefin The MOs and electronic states of carbene have been discussed in 7 The orbital and state correlation diagrams for addition of :CH2 to ethylene is shown in Figure 149.

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