CUMULATIVE REACTION PROBABILITY VIA TRANSITION STATE WAVE PACKETS
CUMULATIVE REACTION PROBABILITY VIA TRANSITION STATE WAVE PACKETS
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DOI：
10.1063/1.471302
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发表时间：
1996-04
影响因子：
4.4
通讯作者：
Dong H. Zhang;J. Light
中科院分区：
文献类型：
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作者：
Dong H. Zhang;J. Light
根据Miller和他的同事给出的著名公式[J.Chem]，发展了一种新的依赖于时间的累积反应概率N(E)方法。太棒了。79,4889(1983)]，N(E)=[(2π)2/2]tr[δ(E−H)Fδ(E−H)F]。利用通量算符只有两个非零本征值的事实，我们利用第一通量算符本征态与分割面(内态)上的哈密顿本征态的直积基来有效地计算迹。由于微正则密度算符δ(E−H)将消除能量远高于总能量E的内态对N(E)的贡献，因此我们可以通过选择内态密度最低的分割面来最小化所需的内态数目。如果分割面位于渐近区域，则只需包含所有开放通道，即内能低于总能量的通道。利用δ(E−H)的傅里叶变换，我们可以得到信息。
A new time‐dependent approach to the cumulative reaction probability, N(E), has been developed based on the famous formulation given by Miller and co‐workers [J. Chem. Phys. 79, 4889 (1983)], N(E)=[(2π)2/2] tr[δ(E−H)Fδ(E−H)F]. Taking advantage of the fact that the flux operator has only two nonzero eigenvalues, we evaluate the trace efficiently in a direct product basis of the first flux operator eigenstates and the Hamiltonian eigenstates on the dividing surface (internal states). Because the microcanonical density operator, δ(E−H), will eliminate contributions to N(E) from an internal state with the energy much higher than the total energy E, we can minimize the number of internal states required by choosing a dividing surface with the lowest density of internal states. If the dividing surface is located in an asymptotic region, one just needs to include all the open channels, i.e., with internal energy lower than the total energy. Utilizing the Fourier transform for δ(E−H), we can obtain the informatio...