正丙醇和异丙醇的紫外光解动力学

利用高里德堡态氢原子飞行时间(HRTOF)探测技术,研究了正丙醇和异丙醇的紫外光解动力学过程.在193.3 nm光辐射下,O-H键快速断裂过程构成主要的氢原子生成通道.伴随O-H键的碎裂,相当大的一部分能量转换成氢原子及其相应碎片的平动能(正丙醇〈fv〉=0.76; 异丙醇〈fv〉=0.78).氢原子碎片具有各向异性的角度分布;其角分布异向因子β分别为-0.79(正丙醇)和-0.77(异丙醇).研究结果表明,吸收1个193.3 nm光子后,丙醇分子跃迁到一个寿命很短的电子激发态;沿着O-H反应坐标,该激发态势能面是排斥的,因而O-H键快速断裂.此外,还得到了丙醇的O-H键离解能: (432±2)kJ/mol(正丙醇)和(433±2)kJ/mol(异丙醇).

Ultraviolet Photodissociation Dynamics of 1-Propanol and 2-Propanol by High-n Rydberg-Atom Time-of-flight(HRTOF) Technique

193.3 nm photodissociation dynamics of jet-cooled 1-propanol and 2-propanol has been examined by using high-n Rydberg-atom time-of-flight (HRTOF) technique. Isotope labeling study indicates that O-H bond fission is the primary H-atom production channel. Center-of-mass (CM) product translational energy release of this channel is large, with 〈fT〉= 0.76 for H+1-propoxy and 0.78 for H+2-propoxy. Maximum CM translational energy release yields an upper limit of the O-H bond dissociation energy: (432±2)kJ/mol in 1-propanol and (433±2)kJ/mol in 2-propanol. H-atom product angular distribution is anisotropic (with β≈-0.79 for 1-propanol and -0.77 for 2-propanol), indicating a short excited-state lifetime. The 193.3 nm H-atom dissociation of both 1-propanol and 2-propanol is prompt and occurs on a repulsive excited-state potential energy surface.