Abstract
Within the generalized gradient approximation (GGA), a calculation of the electronic structure of a semiorganic crystal named bis-thiourea cadmium chloride (BTCC) was performed, then the linear and nonlinear optical responses were obtained over a wide energy range, using a scissor energy of 1.30eV, and our results are in good agreement with the experiments. The accurate full-potential projected augmented wave (FP-PAW) method was used. The prominent spectrum of the second harmonic generation (SHG) was successfully correlated with the dielectric function in terms of single- and double-photon resonances. Both the virtual electron (VE) and virtual hole (VH) processes make contributions to the SHG of BTCC crystal, and the VH process is enhanced by the Cd-centered tetrahedron. The SHG effect of the semiorganic material is attributed to the charge transfer (CT). The CT model for the semiorganic crystal is named as “M-ΠO⋯X”. “M” is a metal atom providing electrons, “ΠO” is a π-conjugated covalent of an organic molecule, and “X” is a high electronegativity atom. The CT across the BTCC molecule is along a π-electron conjugation covalence bond, and the delocalized electrons of sulfur provide an excellent bridge. The strong “pull” effect for the CT is due to the intramolecular hydrogen bonds provided by the chlorine with the high electron affinity.