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首页> 外文期刊>The Journal of Chemical Physics >The electronic spectrum and photodissociation of dinitrogen tetroxide (N_2 O_4): Multireference configuration interaction studies
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The electronic spectrum and photodissociation of dinitrogen tetroxide (N_2 O_4): Multireference configuration interaction studies

机译：四氧化二氮（N_2 O_4）的电子光谱和光解离：多参考构型相互作用研究

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Multireference configuration interaction (MRCI) calculations were performed for vertical excitation energies and potential curves of N_2 O _4 in D2h symmetry using the TZVPP basis set with diffuse functions on the nitrogens. The strong absorption of N_2 O_4 around 185 nm is assigned to the transition from the ground state to 1 B1 1u (σ_O → σ _(N-N)) rather than 1 B1 2u (π _O → π _(NO2),n→ σ N-N), as previously assumed. (N_2 O_4 is placed in the yz-plane, with N-N along z.) Transition to 1 B1 1u is calculated to have an oscillator strength f=0.71 and is z-polarized, in agreement with the experimental observations. Another state, 2 B1 2u, lies close by, however, at a much lower f -value. The weak absorption around 340 nm is assigned to 1 B1 3u. Excitation to 1 B1 2u is calculated at 227 nm. There is no clear assignment of a state for the observed shoulder around 260 nm. TD-DFT (time-dependent density functional theory) vertical excitation energies are close to MRCI values. MRCI singlet and triplet potential curves for the dissociation N_2 O_4 →2 NO_2, combined with a table of NO_2 states correlating with those of N_2 O_4, indicate possible products of photodissociation at various wavelengths. The extensive literature on the photodissociation of N_2 O_4 is reviewed. DFT geometry optimizations have been performed on low-lying singlet and triplet states.
机译：使用带有氮扩散函数的TZVPP基集，对D2h对称的N_2 O _4的垂直激发能和电势曲线进行了多参考配置相互作用（MRCI）计算。 N_2 O_4在185 nm附近的强吸收被指定为从基态到1 B1 1u（σ_O→σ_（NN））的跃迁，而不是1 B1 2u（π_O→π_（NO2），n→σNN ），如先前假设。 （将N_2 O_4放置在yz平面中，其中N-N沿z。）与实验观察一致，计算出向1 B1 1u的跃迁具有振子强度f = 0.71并为z极化。但是，另一状态2 B1 2u处于较低的f值附近。 340 nm附近的弱吸收被指定为1 B1 3u。在227 nm处计算出对1 B1 2u的激发。对于260 nm附近的观察肩部，没有明确分配状态。 TD-DFT（随时间变化的密度泛函理论）垂直激发能接近MRCI值。离解N_2 O_4→2 NO_2的MRCI单重态和三重态电位曲线，与与N_2 O_4的态相关的NO_2状态表结合起来，表明了在各种波长下光解的可能产物。综述了有关N_2O_4光解离的大量文献。 DFT几何优化已在低洼的单重态和三重态下执行。

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