Investigation of hydrogen bond effects on the hyperpolarizability of 2-Aminopyridinium maleate (2APM) complex and determining the non-linear optical susceptibility of the molecular crystal of 2APM

2-Aminopyridinium maleate (2APM) is a recently discovered organic acid-base complex that crystallizes in a non-centrosymmetric space group Pc and hence has a nonzero second-order optical susceptibility. In 2APM the cation (aminopyridinium ion) is connected to the anion (maleate ion) through hydrogen bonds (N1-H10–O2 and N2-H12–O1), we have calculated the molecular properties of 2APM for varying strength of these hydrogen bonds. It is observed that the molecular hyperpolarizabilty varies for varying strength of these hydrogen bonds. These observations are interpreted in terms of the change in nature of the hydrogen bond interaction as its strength is varied. Macropscopic second-order optical susceptibility (d ₀) of 2APM is obtained using the calculated value of molecular hyperpolarizability and the reported crystal structure of 2APM. In order to study the influence of molecular packing on the macroscopic non-linear optical property of the crystal, susceptibility calculations are repeated for 2-methyl-4nitroaniline (MNA) crystal, which is a very well known non-linear optical organic crystal with an exceptionally high value of second-order optical susceptibility. A comparison between the non-linear optical property of 2APM and MNA crystals is given. Comparing the values of d ₀ of 2APM crystals with that of urea shows that the nonlinear optical response of 2APM crystals will be nearly 10 times that of a urea crystal.