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GENERALIZATIONS FOR INTERMOLECULAR INTERACTIONS Equations (333), (334), (338), and (339) are valid under the condition that the perturbation be weak compared to energy di erences, that is, jhAB a eA eB j f 1 The case 1 and case 2 studies revealed the situation in the degenerate case We now interpolate the intermediate situation, remembering that overlap will not be zero except when dictated to be so by local symmetry However, overlap will always be small when dealing with interactions between molecules Refer to Figures 31 34 for the de ned quantities Generalization 1: he L e he U The destabilization of the upper MO relative to the higher energy interacting orbital is approximately the same as the stabilization of the lower MO relative to the lower energy interacting orbital Generalization 2: jhe L j H jhe U j.



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Schwider, 1993

The destabilization of the upper MO relative to the higher energy interacting orbital is always greater than the stabilization of the lower MO relative to the lower energy interacting orbital This is a direct consequence of nonzero overlap [see equation (345)] Generalization 3: (jhe U j C jhe L j) H jhe L j, jhe U j The magnitude of the di erence j between destabilization and stabilization is small compared to the actual magnitudes of the stabilization and destabilization Generalization 4: hAB e k (e A B e B )SAB (k a Positive Constant, SAB Assumed Positive) The interaction matrix element is not precisely proportional to the overlap integral but the behavior with respect to distance and symmetry is essentially the same In other words, hAB will be zero by symmetry when SAB is zero by symmetry, but not otherwise.





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Also, hAB decreases in magnitude as a function of increasing separation in much the same way as SAB Thus, two orbitals will not interact if they behave di erently toward local elements of symmetry The proportionality to the sum of unperturbed orbital energies [see also equation (344)] may be misleading Large negative values for orbital energies are associated with core orbitals for which the overlap is close to zero..

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Figure 6.16. Diagrammatic overview of COSY 2-D NMR experiment. After a preparation period, sample is exposed to three pulses of radiofrequency (RF) radiation with various time delays. The rst pulse is followed by an evolution period (t1 ) which varies from 0 to t1 max . The second pulse is followed by a mixing period ( m ), while a detection period (t2 ) follows the third pulse. FIDs are collected for each value of t1 and produce a two-dimensional time domain data matrix, s(t1 , t2 ). This is Fourier transformed rst with respect to t2 . This produces a one-dimensional spectrum in which the peak amplitude varies regularly as a cosine function of t1 . A second Fourier transform is then performed with respect to t1 to produce a two-dimensional spectrum ( 1 , 2 ). The diagonal of this plot is identical to a one-dimensional NMR spectrum. For simplicity, the spectrum from a single NMR resonance is presented. If multiple resonances were present, correlation effects would be detected as spots off the diagonal ( 1 = 2 ).

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