Effect of the overall rotation on the cis-trans isomerization of HONO induced by an external field.
Effect of the overall rotation on the cis-trans isomerization of HONO induced by an external field.
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DOI：
10.1039/c2cp23709a
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发表时间：
2012-02
期刊：
影响因子：
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通讯作者：
M. Sala;F. Gatti;D. Lauvergnat;H. Meyer
中科院分区：
文献类型：
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作者：
M. Sala;F. Gatti;D. Lauvergnat;H. Meyer
计算了HONO的振转本征能，并与文献中可用的实验能量进行了比较。对于他们的计算，我们使用以前开发的势能面（PES）和一个新推导的精确动能算子（KEO），包括在非正交坐标系中的四原子分子的整体旋转。此外，我们使用海德堡多配置时间相关哈特里（MCTDH）包。我们比较了文献中HONO的实验振转本征值与MCTDH和先前开发的势能面（PES）[F. Richter等人，化学物理学杂志，2004，120，1306.]对于顺式几何形状。在我们以前对HONO [F. Richter等人，化学物理学杂志，2007，127，164315.]导致HONO顺式→反式异构化。发现这种对该过程的影响是弱的。
Rovibrational eigenenergies of HONO are computed and compared to experimental energies available in the literature. For their computation, we use a previously developed potential energy surface (PES) and a newly derived exact kinetic energy operator (KEO) including the overall rotation for a tetra-atomic molecule in non-orthogonal coordinates. In addition, we use the Heidelberg Multi-Configuration Time-Dependent Hartree (MCTDH) package. We compare the experimental rovibrational eigenvalues of HONO available in the literature with those obtained with MCTDH and a previously developed potential energy surface (PES) [F. Richter et al., J. Chem. Phys., 2004, 120, 1306.] for the cis geometry. The effect of the overall rotation on the process studied in our previous work on HONO [F. Richter et al., J. Chem. Phys., 2007, 127, 164315.] leading to the cis→trans isomerization of HONO is investigated. This effect on this process is found to be weak.