《中高层大气物理学》第三章 1 Photochemistry光化学.ppt

LOGO PHYSICS OF THE MIDDLE AND UPPER ATMOSPHERE中高层大气物理学Photochemistry Institute of Space Physics and Applied Technology 2011 Photoionization and Dissociation Photonionization N2 + h? (796A) ? N2+ + e O2 + h? (1026A) ? O2+ + e O + h? (911A) ? O+ + e Dissociative Ionization N2 + h? (510A) ? N+ + N + e O2 + h? (662A) ? O+ + O + e Photondissociation O2 + h? (2422A) ? O + O Photoionization Three major thermospheric species The wavelength specified here correspond to the ionization threshold energy for the production of ions in their ground electronic state. The photoionization rate of species j at altitude z is The branching ratios pj(λ, l) identify production of ions in various electronically excited states, l, or in the ground state. Dissociative ionization: by photons with sufficient energy to both ionize and dissociate the molecule are required. Photodissociation 从双原子分子结构看，分子内部势能是两原子核间距离的函数。 处于稳定态的分子，其两原子核间距离在势能极小值所对应的距离Rc附近。 通常，分子处于ν = 0, 1, 2 · · · 的核间振动状态，两个原子束缚在一起。 当受外界激发时，如太阳辐射照射、分子吸收光能等，核间距离变大。当超过一定的值之后，两个原子分离为独立状态，称为光分解(photodissociation)。 Photodissociation 所谓光分解的“阈值”，是指从分子最小势能状态，到使其两原子分离所需的最小能量。 由于分子的初始振动状态不同（ν不同），要使它分解所需的能量也不同。一般的，把分解基态分子（ν = 0）所需的能量，定义为分解（位势）能。 处于基态的分子被分解为两个原子所需的分解能量为DP1，按分解后原子所处的不同状态，还可以有DP2等其他分解能。 光分解时，入射辐射的能量，一部分使分子分解，其余部分转变为分解后原子的动能或激发能（使原子处于激发态）。 Photodissociation The dissociation threshold energy of O2 is only 5.12 eV so that photon at wavelengths less than 2422A are effective. O2 + h? (2422A) ? O + O Taking account of the entire spectral range, the rate of photodissociation at altitude z is The short wavelength limit is 650A corresponding to the photoionization limit. Photodissociation also leads to different excited states of the products: The excitation energy of O(1D) state is 1.97 eV. The solar irradiance below 1800A (1.97eV) is absorbed by O2 in the thermosphere. Therefore the photodissociation of O2 in the thermosphere is a copious source of excited O atoms. Photodissociation The dissociation of O2 is the first step p