A time-independent theory of photodissociation based on polynomial propagation
A time-independent theory of photodissociation based on polynomial propagation
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DOI：
10.1063/1.475629
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发表时间：
1998-02-08
影响因子：
4.4
通讯作者：
Guo, H
中科院分区：
文献类型：
--
作者：
Guo, H
在多项式传播的框架下，对Heller的分子光解的含时量子理论进行了重新表述。新的配方保留了时间依赖的方法的基本特征，但既不需要传播的时间，也不插值的演化算子。在这种新的方法中，传播是通过递归相应的正交多项式，这需要最小的存储。波包可以被限制到真实的空间，进一步减少了CPU和存储器的需求。如果波包由切比雪夫算子传播，则总截面可以通过余弦傅里叶变换从阶相关自相关函数获得。与含时方法一样，碎片的内部态分布也可以从渐近波包中投影出来。以具有两个活性维度的碘甲烷的非绝热光解离为例说明了新方法的适用性。(C)1998年美国物理学会。
The time-dependent quantum theory of molecular photodissociation of Heller is reformulated in the framework of polynomial propagation. The new formulation retains the essential features of the time-dependent approach, but requires neither propagation in time nor interpolation of the evolution operator. In this new approach, the propagation is carried out by recursion of the corresponding orthogonal polynomial, which requires minimal storage. The wave packet can be restricted to real space, further reducing cpu and memory requirements. If the wave packet is propagated by the Chebyshev operator, the total cross section can be obtained via the cosine Fourier transform from the order-dependent autocorrelation function. Like the time-dependent approach, the internal state distributions of the fragment can be projected out from the asymptotic wave packet. The nonadiabatic photodissociation of methyl iodide with two active dimensions is employed to illustrate the applicability of the new approach. (C) 1998 American Institute of Physics.