A theoretical study of the proton transfer process in the spin-forbidden reaction (1)HNO((1)A ')+OH(-) -> (3)NO(-)((3)Sigma(-))+H(2)O

作者：Lue LingLing^*; Wang XiaoFang; Wang YongCheng; Dai GuoLiang

来源：Chinese Science Bulletin, 2008, 53(10): 1489-1496.

DOI：10.1007/s11434-008-0094-y

• nitroxyl(HNO)
• intersystem crossing
• spin-orbit coupling
• proton transfer reaction

The spin-forbidden reaction (1)HNO((1)A')+OH(-) -> (3)NO(-)((3)Sigma(-))+H(2)O has been extensively explored using various CASSCF active spaces with MP2 corrections in several basis sets. Natural bond orbital (NBO) analysis, together with the NBO energetic (deletion) analysis, indicates that the two isomers have nearly equal total energy and could compete with each other in the title reaction. More significantly, the singlet/triplet surface crossing regions have been examined and the spin-orbit coupling (SOC) and energetics have been computed. The computational results indicate that the SOC is very large at the crossing point T(1)/S(0) trans (ca. 40.9 cm(-1)). Moreover, the T(1)/S(0) trans has a low energy of 10.67 kcal/mol relative to that of trans-So. Therefore, the surface crossing to the triplet state seems much more efficient at the T1/S0 trans region along the minimum energy path (MEP), However, The values of single (P(1)(ISC)) and double (P(2)(ISC)) passes estimated at T(1)/S(0) trans show that the ISC occurs with a little probability.

• 出版日期2008-5
• 单位复旦大学; 天水师范学院; 西北师范大学