Ground state, singlet, triplet

The transfer of energy must proceed with net conservation of spin. In the usual case, the acceptor molecule is a ground-state singlet, and its reaction with the triplet state of the sensitizer will produce the triplet state of the acceptor. The mechanism for triplet photosensitization is outlined below ... 

Ab initio molecular orbital calculations for the model systems RCN3S2 (R = H, NH2) show that these dithiatriazines are predicted to be ground state singlets with low-lying triplet excited states (Section 4.4). The singlet state is stabilized by a Jahn-Teller distortion from C2v to Cj symmetry. In this context the observed dimerization of these antiaromatic (eight r-electron) systems is readily understood. 

Compare the geometries of triplet and ground state singlet anthrone. Where do they differ the most Focus on the carbonyl group. Has the CO bond distance altered Does the molecule incorporate a fully-developed CO n bond (as in ground state singlet anthrone), or a single bond (as in phenol) Is the carbonyl carbon planar or puckered Rationalize your observations. 

PPP calculations indicate the lowest triplet state of o-xylylene to be 8000 cm-1 above the ground state singlet. 

For a triplet to result, two electrons must have different orbitals and the same spin (the Pauli principle forbids having two unpaired electrons in the same orbital since all four quantum numbers would be the same). We saw in Chapter 1 that upon light absorption an electron is promoted from one orbital to a higher orbital. If we were to excite directly from the ground state singlet to the triplet state we would have to simultaneously change orbitals and electronic spins. Since this process is relatively improbable, direct absorption to the triplet state is seldom observed (later in this chapter,... 

Singlet oxygen C ) differs from the predominant oxygen molecule in that O2 is in the ground state or triplet state and its outer two unshared electrons have parallel spins (sometimes designated 302), which is nearly unreactive toward other molecules, while singlet oxygen... 

The susceptibility of a carbene to reaction with oxygen can be used as a probe of its spin multiplicity. If a carbene is insensitive to oxygen, this is taken to be an indication that it is a ground-state singlet and that the singlet does not readily form the triplet carbene. 

At distances less than 10 A between donors and acceptors, triplet-triplet energy transfer becomes important. Triplet-triplet energy transfer between excited-state triplet donors (D ) and ground-state singlet acceptors (A) proceeds according to the reaction... 

By analogy with the mechanism proposed for the reaction with alkenes, C—H insertion product formation can be explained in terms of a H abstraction-recombination process of triplet arylcarbenes. The observations that ground-state singlet carbenes, for example, chlorophenylcarbene (67), produce only O—H insertion... 

The role of spin in the reaction is an especially interesting and important issue in carbene chemistry. Apparent violation of the spin selection rule, such as the reaction of ground state singlet carbene with triplet molecular oxygen in matrices as well as in solution, and the reaction of triplet ground-state carbenes with (singlet) CO, CO2, and N2 in matrices, are challenging issues for the near future. 

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