Bond energy normalized molecules

Once the BEs and SBEs have been decided upon, the normal functioning of the MM program causes each bond to be multiplied by the number of times it appears in the computed molecule to find its contribution to the total bond enthalpy. In ethylene, 26.43 + 4(—4.59) = 8.07kcalmol . In Eile Segment 5-1, this sum is denoted BE. This whole procedure is essentially a conventional bond energy calculation. 

The meaning of the word aromaticity has evolved as understanding of the special properties of benzene and other aromatic molecules has deepened. Originally, aromaticity was associated with a special chemical reactivity. The aromatic hydrocarbons were considered to be those unsaturated systems that underwent substitution reactions in preference to addition. Later, the idea of special stability became more important. Benzene can be shown to be much lower in enthalpy than predicted by summation of the normal bond energies for the C=C, C—C, and C—H bonds in the Kekule representation of benzene. Aromaticity is now generally associated with this property of special stability of certain completely conjugated cyclic molecules. A major contribution to the stability of aromatic systems results from the delocalization of electrons in these molecules. 

For a given molecule and a given intemuclear separation a would have a definite value, such as to make the energy level for P+ lie as low as possible. If a happens to be nearly 1 for the equilibrium state of the molecule, it would be convenient to say that the bond is an electron-pair bond if a is nearly zero, it could be called an ionic bond. This definition is somewhat unsatisfactory in that it does not depend on easily observable quantities. For example, a compound which is ionic by the above definition might dissociate adiabatically into neutral atoms, the value of a changing from nearly zero to unity as the nuclei separate, and it would do this in case the electron affinity of X were less than the ionization potential of M. HF is an example of such a compound. There is evidence, given bdow, that the normal molecule approximates an ionic compound yet it would dissociate adiabatically into neutral F and H.13... 

The Structures of Simple Molecules.—The foregoing considerations throw some light on the structure of very simple molecules in the normal and lower excited states, but they do not permit such a complete and accurate discussion of these questions as for more complicated molecules, because of the difficulty of taking into consideration the effect of several unshared and sometimes unpaired electrons. Often the bond energy is not great enough to destroy s-p quantization, and the interaction between a bond and unshared electrons is more important than between a bond and other shared electrons because of the absence of the effect of concentration of the eigenfunctions. 

Although standard enthalpies of formation provide information about the net stability of molecules and their transformations, they do not always indicate stability of individual bonds. This analysis normally involves parameters, loosely called bond energies, that reflect the amount of energy required to cleave chemical bonds. 

For this case, the primary change that is observable in the IR spectrum is due to changes in the vibrahonal frequencies of the probe molecule due to modificahons in bond energies. This can lead to changes in bond force constants and the normal mode frequencies of the probe molecule. In some cases, where the symmetry of the molecule is perturbed, un-allowed vibrational modes in the unperturbed molecule can be come allowed and therefore observed. A good example of this effect is with the adsorption of homonuclear diatomic molecules, such as N2 and H2 (see Section 4.5.6.8). 

Any bond energy formula can be expressed either i) by reference to a selected bond with reference net atomic charges q and q°i at the bond-forming atoms k and I, or ii) by reference to hypothetical k-l bonds constructed with the assumption q = q° = 0. The former reflects a physical situation, but requires additional work in order to sadly charge normalization constraints it is most useful in the constmction of general energy formulas for molecules that use chemical shifts espressed with respect to the appropriate references. The latter method simplifies bond-by-bond calculations. The two forms are... 

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