Baloïtcha Ezinvi, Balint-Kurti Gabriel G
Centre for Computational Chemistry, School of Chemistry, University of Bristol, Bristol, UK BS8 1TS.
Phys Chem Chem Phys. 2005 Nov 21;7(22):3829-33. doi: 10.1039/b511640f. Epub 2005 Sep 20.
The effect of vibrational excitation on the photodissociation cross section of ozone in the Hartley continuum is examined. The calculations make use of newly computed potential energy and transition dipole moment surfaces. The initial vibrational states of the ozone are computed using grid based techniques and the first few ab initio computed vibrational energy level spacings agree to within 10 cm(-1) with experimental values. The computed total absorption cross sections arising from different initial vibrational states of ozone are discussed in the light of the nature of the transition dipole moment surface. The computed cross section for excitation from the ground vibrational-rotational state is in good agreement with the experimentally measured cross section. Excitation of the asymmetric stretching vibration of ozone has a marked effect on both the form and magnitude of the photodissociation cross section. The velocity distributions of highly reactive O(1D) atoms arising from the photodissociation process in different wavelength ranges is also presented. The results show that the O(1D) atoms travel with a most probable translational velocity of 2.030 km s(-1) corresponding to a translational energy of 0.342 eV or 33.0 kJ mol(-1).
研究了振动激发对哈特利连续谱中臭氧光解离截面的影响。计算使用了新计算的势能和跃迁偶极矩面。臭氧的初始振动态使用基于网格的技术进行计算，从头计算得到的前几个振动态能级间距与实验值在10 cm⁻¹范围内相符。根据跃迁偶极矩面的性质，讨论了由臭氧不同初始振动态产生的计算总吸收截面。从基振转态激发的计算截面与实验测量截面吻合良好。臭氧不对称伸缩振动的激发对光解离截面的形式和大小都有显著影响。还给出了不同波长范围内光解离过程产生的高活性O(¹D)原子的速度分布。结果表明，O(¹D)原子以最概然平动速度2.030 km s⁻¹运动，对应平动能0.342 eV或33.0 kJ mol⁻¹。
