The Molecular Orbital Approach to Colour and Constitution

The potential value of the application of molecular orbital methods in colour chemistry is immense. In essence, the reason for this is that the methods enable, in principle, many of the light absorption properties of dyes, from a knowledge of their chemical structure, to be calculated with the aid of a computer. Thus, the colour properties of any dye whose structure may be drawn on paper may be predicted, with some expectation of accuracy, without the need to resort to devising a method for the 

The PPP-MO method is suitable for the treatment of large molecules, does not present major computing demands and programs are now routinely used as a tool to calculate the colour properties of dyes. Unlike the HMO method, it handles heteroatomic species well. The method has been remarkably successful in calculating /lmax values for a wide range of dyes from virtually all of the chemical classes. For example, the method provides a reasonably accurate account of substituent effects in the range of aminoazobenzene dyes, including compounds 15a-f and 16a-f which have been discussed in terms of the valence-bond approach in the previous section of this chapter. 

Some n-electron charge density differences between the ground and first excited states calculated by the PPP-MO method for 4-aminoazobenzene, 

The direction of the transition moment is of practical consequence in dyes used in liquid crystal display systems. It is important for such applications that the direction of the transition moment is aligned with the molecular axis of the dye. Since this is the case with azo dye 15f, the dye would appear to be a reasonable candidate as a liquid crystal display dye (see Chapter 10 for further discussion of this application of dyes). 

The intensity of colour of a dye is dependent on the probability of the electronic transition. A familiar example of this principle is provided by 

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