Vibrational Versus Electronic (hyper)polarizabilities of Conjugated Organic and Inorganic Molecules: Non‐Empirical Investigation

Vibrational and electronic first hyperpolarizabilities have been computed at ab‐initio and non‐empirical levels for two different sets of molecules. The first set contains TICT (Twist Intramolecular Charge Transfer) molecules and the second set encloses nine Ru(II)‐bipyridine complexes. The effect of the interring twist angle on the TICT electrical properties have been studied. It has been found that when this angle increases βe increases and βv remains almost constant between 0° and 65° then increases suddenly to reach a large value at 78° and then decreases again. In the second set, the results show that both contributions to the first hyperpolarizability are affected by the complexation.