Soto Juan, Peláez Daniel, Otero Juan C
Department of Physical Chemistry, Faculty of Science, University of Málaga, Andalucía Tech., E-29071 Málaga, SpainInstitut des Sciences Moléculaires d'Orsay (ISMO) - UMR 8214, Université Paris-Saclay, 91405 Orsay Cedex, France.
Institut des Sciences Moléculaires d'Orsay (ISMO) - UMR 8214, Université Paris-Saclay, 91405 Orsay Cedex, France.
J Chem Phys. 2021 Jan 28;154(4):044307. doi: 10.1063/5.0033181.
The photodissociation channels of nitrosobenzene (PhNO) induced by a 255 nm photolytic wavelength have been studied using the complete active space self-consistent method and the multistate second-order multiconfigurational perturbation theory. It is found that there exists a triplet route for photodissociation of the molecule. The reaction mechanism consists of a complex cascade of nonadiabatic electronic transitions involving triple and double conical intersections as well as intersystem crossing. Several of the relevant states (S, S, and S states) correspond to double excitations. It is worth noting that the last step of the photodissociation implies an internal conversion process. The experimentally observed velocity pattern of the NO fragment is a signature of such a conical intersection.
利用完全活性空间自洽场方法和多态二阶多组态微扰理论，研究了在255 nm光解波长下亚硝基苯（PhNO）的光解离通道。研究发现该分子的光解离存在一条三重态路径。反应机理包括一系列复杂的非绝热电子跃迁，涉及三重和双重锥形交叉以及系间窜越。几个相关态（S、S和S态）对应于双激发。值得注意的是，光解离的最后一步意味着一个内转换过程。实验观测到的NO碎片的速度模式是这种锥形交叉的一个特征。
