An effective model for the X 2A1–A 2B2 conical intersection in NO2
An effective model for the X 2A1–A 2B2 conical intersection in NO2
复制标题
NO2 中 X 2A1–A 2B2 圆锥相交的有效模型
DOI：
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发表时间：
2003
期刊：
影响因子：
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通讯作者：
M. Lombardi
中科院分区：
文献类型：
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作者：
M. Joyeux;R. Jost;M. Lombardi
我们提出了一种有效的计算本征态和调整有效哈密顿量参数的方法，该方法再现了NO2在量子力学基态之上高达11 800 cm−1的实验观测能级，即在X 2A1-A 2B2圆锥形交点之上数千cm−1，其有效值误差小于4 cm−1。该方法主要依赖于通过一阶摄动理论确定每个表面的最优基，该基考虑到该表面的状态所经历的非共振能量位移。因此，为了使光谱收敛到11 800 cm−1，必须建立和对角化的矩阵的大小是500-1000的数量级，而不是几万。由于这个哈密顿量，可以完成高达11 800 cm−1的实验光谱分析。本文对9500 cm−1以上的所有状态进行了详细描述，对9500 cm−1以下的状态进行了描述。
We propose an efficient method for calculating the eigenstates and adjusting the parameters of an effective Hamiltonian, which reproduces the experimentally observed energy levels of NO2 up to 11 800 cm−1 above the quantum mechanical ground state, that is a few thousands of cm−1 above the X 2A1–A 2B2 conical intersection, with a rms error less than 4 cm−1. This method principally relies on the determination, through first-order perturbation theory, of an optimal basis for each surface, which takes into account the nonresonant energy shifts experienced by the states of this surface. As a result, the size of the matrix, which one has to build and diagonalize to converge the spectrum up to 11 800 cm−1, is of the order of 500–1000 instead of several tens of thousands. Thank to this Hamiltonian, the analysis of the experimental spectrum up to 11 800 cm−1 could be completed. A detailed description of all states located above 9500 cm−1 is proposed, those lying below 9500 cm−1 being already known and tabulated.