Abstract
Present investigation demonstrates that push electron effect of nitrogen in M … NH3is reduced rather than enhanced upon lithiation which has been explained by natural bond orbital analysis showing that nitrogen atom in NLi3 changes it's state of hybridization from sp3 to sp2 leaving the 2pz orbital partially occupied. This makes NLi3 a weak acceptor of electrons from alkaline earth metals. When the second alkaline earth metal is introduced the 2pz orbital of nitrogen attains the maximum occupation as a result of cumulative charge transfer from two metal atoms. However, the push electron effect still operates resulting in the diffuse electron localized over the metals. Large enhancement of second hyperpolarizability (106 au) in M … NLi3 has been rationalized by its low lying intense transitions. Effect of basis set on the second hyperpolarizability has been studied at the CCSD level which showed that Sadlej's pol and 6–311++G(3df,3pd) basis sets give comparable results that are obtained for the aug-cc-pVTZ basis set. The results of second hyperpolarizability calculated by using different DFT functionals are found to be consistent with the CCSD results obtained for the aug-cc-pVTZ basis set.
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