Absorption cross section of ozone isotopologues calculated with the multiconfiguration time-dependent hartree (MCTDH) method: I. The Hartley and Huggins bands.
Absorption cross section of ozone isotopologues calculated with the multiconfiguration time-dependent hartree (MCTDH) method: I. The Hartley and Huggins bands.
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使用多构型时间相关哈特里 (MCTDH) 方法计算的臭氧同位素体的吸收截面：I. 哈特利和哈金斯带。
DOI：
10.1021/jp103266m
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发表时间：
2010
期刊：
影响因子：
--
通讯作者：
R. Jost
中科院分区：
文献类型：
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作者：
S. Ndengué;F. Gatti;R. Schinke;H. Meyer;R. Jost
本文计算了臭氧分子的18种同位素在Hartley-Huggins带（27000-55000 cm ~（-1））范围内的吸收截面。所有18种可能的臭氧同位素都是由（16）O、（17）O和（18）O生成的，重点是那些具有物理学意义的同位素，如（16）O（3）（17）O（16）O（2）、（16）O（17）O（16）O、（18）O（16）O（2）和（16）O（18）O（16）O。我们使用MCTDH算法来传播波包。作为一个初始波包，我们采取的振动基态乘以跃迁偶极矩表面。由该波包的自相关函数得到了散射截面。计算中只涉及两个势能面和相应的跃迁偶极矩。解离的R态被省略了。仅对J = 0进行了计算。在模拟转动包络的经验平滑后，与（16）O（3）和（18）O（3）的实验吸收截面进行了比较。18种同位素体的截面的同位素体依赖性可以分成两个能量范围，（a）从27000到32000 cm（-1），Huggins带，其是高度结构化的，和（B）从32000到55000 cm（-1），截面的主要部分，其具有钟形，Hartley带。这个钟形包络线的特点是一个新的分析模型，只依赖于四个参数，振幅，中心，宽度和不对称性。这些参数的同位素体依赖性揭示了各种同位素体的吸收截面之间的微小差异。哈特利带的光滑形状相比，哈金斯带具有明显的振动结构，因此显示出大的同位素差异，这可能会导致显着的同位素依赖性的光化通量下的臭氧光解速率。
The absorption cross sections of 18 isotopologues of the ozone molecule have been calculated in the range of the Hartley-Huggins bands (27000-55000 cm(-1)). All 18 possible ozone isotopologues made with (16)O, (17)O, and (18)O have been considered, with emphasis on those of geophysics interest like (16)O(3) (17)O(16)O(2), (16)O(17)O(16)O, (18)O(16)O(2), and (16)O(18)O(16)O. We have used the MCTDH algorithm to propagate wavepackets. As an initial wavepacket, we took the vibrational ground state multiplied by the transition dipole moment surface. The cross sections have been obtained from the autocorrelation function of this wavepacket. Only two potential energy surfaces (PESs) and the corresponding transition dipole moment are involved in the calculation. The dissociating R state has been omitted. The calculations have been performed only for J = 0. The comparison with the experimental absorption cross sections of (16)O(3) and (18)O(3) has been performed after an empirical smoothing which mimics the rotational envelop. The isotopologue dependence of the cross sections of 18 isotopologues can be split into two energy ranges, (a) from 27000 to 32000 cm(-1), the Huggins band, which is highly structured, and (b) from 32000 to 55000 cm(-1), the main part of the cross section which has a bell shape, the Hartley band. This bell-shaped envelop has been characterized by a new analytic model depending on only four parameters, amplitude, center, width, and asymmetry. The isotopologue dependence of these parameters reveals the tiny differences between the absorption cross sections of the various isotopologues. In contrast to the smooth shape of the Hartley band, the Huggins band exhibits pronounced vibrational structures and therefore shows large isotopologue differences which may induce a significant isotopologue dependence of the ozone photodissociation rates under actinic flux.