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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Comparison of the Huggins band for six ozone isotopologues: Vibrational levels and absorption cross section
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Comparison of the Huggins band for six ozone isotopologues: Vibrational levels and absorption cross section

机译：六个臭氧同位素分子的哈金斯谱带比较：振动能级和吸收截面

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摘要

By use of the 3~1A' ab initio potential energy surface (PES) of ozone and the multi-configuration time-dependent Hartree program for wavepacket propagation, we have determined numerous eigenstates of this state for six ozone isotopologues. These bound vibrational levels are the upper levels of the Huggins band, which covers the range from 27 000 to ～33 000 cm~(-1). This study extends our previous work on the Hartley band, which was limited to the range ～32 000-50 000 cm~(-1). Four isotopologues, ~(16)O_3, ~(16)O~(17)O~(16)O, ~(16)O~(18)O~(16)O, and ~(18)O_3 (noted hereafter 666, 676, 686, and 888), are symmetric, and two are asymmetric, ~(17)O~(16)O_2 and ~(18)O~(16)O _2 (noted hereafter 667 and 668). The PES of the 3~1A' state has two equivalent minima of C_s symmetry located at ～27 000 cm~(-1) above the X~1A_1 ground state. The equilibrium geometry of these two minima is re1 = 2.28 a0, re2 = 3.2 a0, and θe = 107°. The dissociation limit of this PES, which correlates to the O(~1D) + O_2 (~1Δ) "singlet" channel, is about 4300 cm~(-1) above the two minima. For the ~（16）O_3 isotopologue, the 120 lowest bound eigenstates have been calculated and partially assigned up to 800 cm-1 below the dissociation limit. The 60 lower eigenstates are easily assignable in term of three normal modes, the "long" bond (ν_1), the bending (ν_2), and the "short" bond (ν_3). A new family of wave functions, aligned along the dissociation channels, appears at 3782 cm~(-1) above the 3~1A' (0,0,0) level. The 3~1A' vibrational levels and the corresponding intensity factors from the (000), (010), (100), and (001) levels of the X~1A_1 ground state have been calculated for the six isotopologues. The Huggins absorption cross sections of the six isotopologues have been calculated from the 3~1A' vibrational energy levels and the corresponding intensity factors. The rotational envelope of each vibronic band has been empirically described by an ad hoc function. The ratio of the Huggins cross section of each ozone isotopologue with one of ~(16)O_3 provides the fractionation factor of each ozone isotopologue as a function of the photon energy. These various fractionation factors will allow predicting enrichments due to photolysis by various light sources like the actinic flux.
机译：通过使用臭氧的3〜1A'从头计算势能面（PES）和随时间变化的基于多组态的Hartree程序进行波包传播，我们为6个臭氧同位素分子确定了该状态的许多本征态。这些有限的振动水平是哈金斯带的上限，覆盖范围从27 000〜〜33000 cm〜（-1）。这项研究扩展了我们先前在Hartley波段上的工作，该波段仅限于〜32 000-5 000 cm〜（-1）。 〜（16）O_3，〜（16）O〜（17）O〜（16）O，〜（16）O〜（18）O〜（16）O和〜（18）O_3四个同位素（666、676、686和888）是对称的，两个是不对称的〜（17）O〜（16）O_2和〜（18）O〜（16）O_2（以下称为667和668）。 3〜1A'状态的PES具有两个等效的C_s对称极小值，位于X〜1A_1基态以上〜27000 cm〜（-1）。这两个最小值的平衡几何形状分别为re1 = 2.28 a0，re2 = 3.2 a0和θe= 107°。与O（〜1D）+ O_2（〜1Δ）“单峰”通道相关的该PES的解离极限在两个最小值之上约4300 cm〜（-1）。对于〜（16）O_3同位素，已计算出120个最低结合本征态，并在离解离极限以下800 cm-1处被部分分配。 60个较低的本征态可以通过三种正常模式轻松分配：“长”键（ν_1），弯曲（ν_2）和“短”键（ν_3）。沿解离通道排列的新的波函数族出现在3〜1A'（0,0,0）水平上方的3782 cm〜（-1）处。计算了六个同位素分子的3〜1A'振动能级以及X〜1A_1基态的（000），（010），（100）和（001）能级的相应强度因子。根据3〜1A'的振动能级和相应的强度因子，计算了六个同位素的Huggins吸收截面。每个振动带的旋转包络已通过ad hoc函数进行了经验描述。每个臭氧同位素分子的Huggins横截面与〜（16）O_3之一的比率提供了每个臭氧同位素分子的分馏因子，该因子是光子能量的函数。这些不同的分馏因子将允许预测由于诸如光化通量之类的各种光源的光解而引起的富集。

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