Unpairing

Hund s rules Rules which describe the electronic configuration of degenerate orbitals in the ground state. The electronic configuration will have the maximum number of unpaired... 

Electron Spin Resonance Spectroscopy. Several ESR studies have been reported for adsorption systems [85-90]. ESR signals are strong enough to allow the detection of quite small amounts of unpaired electrons, and the shape of the signal can, in the case of adsorbed transition metal ions, give an indication of the geometry of the adsorption site. Ref. 91 provides a contemporary example of the use of ESR and of electron spin echo modulation (ESEM) to locate the environment of Cu(II) relative to in a microporous aluminophosphate molecular sieve. 

The two primary causes of shielding by electrons are diamagnetism and temperature-independent paramagnetism (TIP). Diamagnetism arises from the slight unpairing of electron orbits under the influence of the magnetic field. This always occurs so as to oppose the field and was first analysed by Lamb [7]. A simplified version of his fomuila. 

Paramagnetic s 102-10 Interaction with isolated unpaired electrons... 

The negative sign in equation (b 1.15.26) implies that, unlike the case for electron spins, states with larger magnetic quantum number have smaller energy for g O. In contrast to the g-value in EPR experiments, g is an inlierent property of the nucleus. NMR resonances are not easily detected in paramagnetic systems because of sensitivity problems and increased linewidths caused by the presence of unpaired electron spins. 

ENDOR transitions can be easily understood in temis of a simple system consisting of a single unpaired electron spin (S=2) coupled to a single nuclear spin (1=2). The interactions responsible for the various... 

Wliile the earliest TR-CIDNP work focused on radical pairs, biradicals soon became a focus of study. Biradicals are of interest because the exchange interaction between the unpaired electrons is present tliroiighoiit the biradical lifetime and, consequently, the spin physics and chemical reactivity of biradicals are markedly different from radical pairs. Work by Morozova et al [28] on polymethylene biradicals is a fiirther example of how this method can be used to separate net and multiplet effects based on time scale [28]. Figure Bl.16.11 shows how the cyclic precursor, 2,12-dihydroxy-2,12-dimethylcyclododecanone, cleaves upon 308 mn irradiation to fonn an acyl-ketyl biradical, which will be referred to as the primary biradical since it is fonned directly from the cyclic precursor. The acyl-ketyl primary biradical decarbonylates rapidly k Q > 5 x... 

Paramagnetism implies the presence of single, unpaired, electrons. Hence nitrogen oxide is paramagnetic and so is any other molecule or ion containing unpaired electrons. If the total number of electrons in an ion or molecule is odd. then it must be paramagnetic but some molecules (e.g. Oj and ions have an even number of electrons and yet are paramagnetic because some of them are unpaired. 

The structure of nitrogen dioxide contains an unpaired (odd) electron and the molecule is consequently paramagnetic. The odd electron is not localised on any atom and the structure can be best represented as a resonance hybrid of the structures ... 

Oxygen is a colourless gas which condenses to a pale blue liquid, b.p. 90 K, which is markedly paramagnetic indicating the presence of unpaired electrons (p. 229). Simple valence bond theory (as used in this book) would indicate the structure... 

The ions and have 7 and 6 d electrons respectively. Where there are orbitals of the same (or nearly the same) energy, the electrons remain unpaired as far as possible by distributing themselves over all the orbitals. In the case of [CofNHj) ] -, the energy split in the d orbitals due to octahedral attachment of the six... 

Above all, spin density is most significant for radicals. Their unpaired electrons can be localized rapidly, by visualizing this property on the molecule. 

Closed-sh ell molecules h ave a multiplicity of on e (a sin glet),. A radical, with one unpaired eleetroti, has a spin multiplieity of two (a donblet), A 111olecular system with two uii paired electron s (nsnally... 

Closed-sh ell inolceiiles h avc a multiplicity of on c (a sin glet), A radical, with on e un paii ed deetroii, h as a m ultiplieity of two (a doublet),. A iTiolceiilar system with two unpaired eleelrons (usually a triplet) has a m u Itip licity o f ihrec. In some cases, however, such as a biradieal, two unpaired electrons may also be a singlet. 

Notice lh il Ihc orbiuls nc riol paiied, >.(/i"does n ol liiivc Ihc siimc energy as An unrestricted wave ftinction like this is a natural way of representing system s with unpaired electron s, such as the doublet shown here or a triplet state ... 

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