We present for the first time an exact quantum study of spin-orbit-induced intersystem crossing effects in the title reaction. The time-dependent wave-packet method, combined with an extended split operator scheme, is used to calculate the fine-structure resolved cross section. The calculation involves four electronic potential-energy surfaces of the 1 AЈ state ͓J. Dobbyn and P. J. Knowles, Faraday Discuss. 110, 247 ͑1998͔͒, the 3 AЈ and the two degenerate 3 AЉ states ͓S. Rogers, D. Wang, A. Kuppermann, and S. Wald, J. Phys. Chem. A 104, 2308 ͑2000͔͒, and the spin-orbit couplings between them ͓B. Maiti, and G. C. Schatz, J. Chem. Phys. 119, 12360 ͑2003͔͒. Our quantum dynamics calculations clearly demonstrate that the spin-orbit coupling between the triplet states of different symmetries has the greatest contribution to the intersystem crossing, whereas the singlet-triplet coupling is not an important effect. A branch ratio of the spin state ⌸ 3/2 to ⌸ 1/2 of the product OH was calculated to be ϳ2.75, with collision energy higher than 0.6 eV, when the wave packet was initially on the triplet surfaces. The quantum calculation agrees quantitatively with the previous quasiclassical trajectory surface hopping study.

A nonadiabatic quantum dynamics calculation involving four coupled potential energy surfaces (two degenerate 3A' ', one 3A', and one 1A') and the spin-orbit coupling matrix for these states is reported for the title reaction. The results show that the important discrepancy between theoretically calculated and experimentally measured intramolecular isotope effects can at least in part be attributed to significant nonadiabatic effects.

A highly luminescent LnMOF {[Eu 2 (bqdc) 3 (H 2 O)(DMF) 3 ]$0.5DMF$H 2 O} n (1, bqdc ¼ 2,2 0 -biquinoline-4,4 0dicarboxylate) was designed and synthesized. It was characterized by single crystal X-ray diffraction, PXRD, TGA, EA and FT-IR. A new strategy for preparing mechanically robust MOF thin films was developed by electrodeposition in combination with subsequent solvothermal synthesis. A portable sensor device prototype consisting of a film of 1 was conveniently fabricated by using this new strategy and this sensor device exhibits a highly selective response to Hg 2+ . Its luminescence quenching can be distinguished clearly with the naked eye when illuminated by a handy UV banknote detector. The diffusion kinetics of Hg 2+ into the LnMOF film is first proposed.