Université de Grenoble 1/CNRS, LIPhy UMR 5588, Grenoble, F-38041, France.
J Phys Chem A. 2012 Dec 20;116(50):12260-70. doi: 10.1021/jp3064382. Epub 2012 Dec 11.
By use of the 3(1)A' 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(1)A' state has two equivalent minima of C(s) symmetry located at ~27,000 cm(-1) above the X(1)A(1) ground state. The equilibrium geometry of these two minima is r(e(1)) = 2.28 a(0), r(e(2)) = 3.2 a(0), and θ(e) = 107°. The dissociation limit of this PES, which correlates to the O((1)D) + O(2) ((1)Δ) "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(1)A' (0,0,0) level. The 3(1)A' vibrational levels and the corresponding intensity factors from the (000), (010), (100), and (001) levels of the X(1)A(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(1)A' 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.
利用臭氧的 3(1)A' 从头势能面 (PES) 和多组态含时哈特ree 波包传播程序，我们确定了六个臭氧同位素的这个态的许多本征态。这些束缚振动能级是 Huggins 带的上限能级，该带覆盖 27000 至约 33000 cm(-1)的范围。这项研究扩展了我们之前对 Hartley 带的研究，该研究仅限于约 32000-50000 cm(-1)的范围。四个同位素，(16)O(3)、(16)O(17)O(16)O、(16)O(18)O(16)O 和 (18)O(3)（此后分别记为 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)（此后分别记为 667 和 668）。3(1)A' 态的 PES 具有两个位于 X(1)A(1)基态以上约 27000 cm(-1)的 C(s)对称等效最小值。这两个最小值的平衡几何形状为 r(e(1)) = 2.28 a(0)，r(e(2)) = 3.2 a(0)，θ(e) = 107°。该 PES 的离解极限，与 O((1)D) + O(2) ((1)Δ)“单重”通道相关联，位于两个最小值上方约 4300 cm(-1)。对于 (16)O(3)同位素，计算了 120 个最低束缚本征态，并在离解极限以下约 800 cm(-1)的范围内部分分配。60 个较低的本征态可以很容易地用三个正则模式来分配，即“长”键（ν(1))、弯曲（ν(2))和“短”键（ν(3))。在 3782 cm(-1)处出现了一组新的波函数，沿着离解通道排列。从 X(1)A(1)基态的 (000)、(010)、(100)和 (001)能级计算了六个同位素的 3(1)A' 振动能级和相应的强度因子。从 3(1)A' 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。对于每个振动带，通过经验函数描述了其旋转包络。每个臭氧同位素的 Huggins 截面与 (16)O(3)之一的比值提供了每个臭氧同位素的分馏因子作为光子能量的函数。这些不同的分馏因子将允许预测各种光源（如光化通量）光解引起的富集。
