Electronic structures and nonlinear optical properties of XAuPH3

The studies on model systems XAuPH₃ (X=H, F, Cl, Br, I, CN, CH₃) have been carried out by using ab intio HF and DFT B3LYP methods at pseudopotential and double-zeta LANL2DZ level. The results are compared with those of MP2. The properties of the models, i.e. the atomic net charge populations, the frontier molecular orbitals and nonlinear optical (NLO) properties have been investigated under an applied electric field on the basis of optimized structures. The computational results show that for these models characterized as electron acceptor-metal-electron donor (A-M-D) system, the NLO properties are due to intramolecular charge-transfer interaction between the acceptor and the donor. The more charges transfer gives, the better NLO properties. In the selected model systems, IAuPH₃ has the biggest βvec and γ of 1184.1942 a.u. and 17341.9214 a.u., whereas IC₆H₄PH₃ ⁺, a typical A-π-D organic conjugated system, has β_vec and γ of 710.7697 and 11664.1405 a.u. respectively. In comparison, IAuPH₃ has significant NLO properties.