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Concise Biochemistry by Anatoly Bezkorovainy

By Anatoly Bezkorovainy

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2 i 1 [121(i 13 2 i + 2 [121(i+2] 2 . + [122(i l)] [122(i+2)] - * . * ... 1 [ [ I ] 1 ...... 3 ...... [ ...... ... ...... ... ...... ... There is one such table for each MO, y A i , and each table is by coiistruction symmetrical. The sum of its terms is indicated as S{mm'},,. T h e diagonal elements of a quadrant are indicated as {mm'}dliand its sum as S(mm'},,i. For m = m', the quadrant {mrn},i contains quantities which are specific to the atomic set for the atom m ; for m # m' the quadrant {mm'),, contains quantities which are specific to atomic sets of the atoms m and m'.

1. Electronic Structure in Molcculcs, Especially in Cyano Compounds T h e quantity 45 D,is the relativistic part of the dissociation energy. , and, therefore, to Q=l discount such terms. LVe do not agree with such a n optimistic approach except for molecules containing first- and possibly secondrow atoms. For molecules containing third-row atoms, we expect D, to have a value of from a few tenths of a calorie u p to a kilocalorie in extreme cases. However, such contributions can be computed safely from perturbation theory.

T h e main correction to these diagrams can be obtained A from atomic computations, more explicitly from associating to the EAoa correction proportional to the (mm)and the atomic correlation less degeneracy effects (see Veillard and Clementi26*27for numerical values). This is a very simple correction to introduce. Alternatively, the correction to ELIocan be computed using the device of correcting the Pij integrals with a pseudopotential (for example, see Clementi’s This alternative is not too different from the previous one, since the pscudopotential uses the overlap between orbitals as a parameter.

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