铑羰基氢化物的量子化学研究

The Quantum Chemical Investigation on the Rhodium Carbonyl Hydride Species

铑羰基氢化物的量子化学研究张华北，胡常伟，田安民，鄢国森（四川大学化学系，成都，６１００６４）关键词铑羰基氢化物，从头算相对论有效芯势，振动光谱，几何结构实验表明，铑能催化合成气加氢形成多种产物［１］，该反应所生成的活性中间物──铑羰基氢化物的红外光...

The electronic and geometric structures,the vibrational frequencies and the intensities of a series of rhodium carbonly hydride species were investigated by use of the ab initio calculation. It was predicted that the rhodium carbonyl hydride species containning 1,2 and 3 hydrogen atoms could exist during the hydrogenation of CO or CO2 on Rh catalyst.H atom was tending to exclude CO out of the systems when the number of H in the system increased. In all the calculated rhodium carbonyl species, the most intensive vibrational mode,the intensity of which increased with increasing H coadsorbed, was caused by Rh-H vibration other than C-O, while an obvious counterside effect usually observed in complex compound was seen in(H)3 RhCO[Cs].The redshift of CO+H2Rh system from 2050 cm-1 to about 2000 cm-1 observed in experiments might be caused by the vibration of Rh-H instead of that of C-O,the intensity of which was predicted to blue shift and diminish with increasing H number in the rhodium carbonyl hydride species.