Toward an improved ground state potential energy surface of ozone.
Toward an improved ground state potential energy surface of ozone.
复制标题
改善臭氧基态势能面。
DOI：
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发表时间：
2010
影响因子：
2.9
通讯作者：
V. Tyuterev
中科院分区：
文献类型：
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作者：
F. Holka;P. Szalay;T. Müller;V. Tyuterev
利用高水平从头算技术对臭氧势能面进行了系统的研究。方法包括icMR-CISD和icMR-AQCC与所有电子相关，使用全价CAS参考空间和基设置为六倍-ζ质量以及外推到完整的基集极限。我们沿着开放（C(2v)）平衡结构周围的拉伸和弯曲坐标，以及包括过渡态和范德华最小区域在内的解离最小能量路径，计算了密集的三维网格和一维切割。对我们结果的详细分析证实了Schinke小组先前的计算，并确保这些计算不会因基集的缺陷、缺乏相对论修正或核心相关效应而产生偏差。最后，我们讨论了可能的误差来源，可以解释与实验结果相比的剩余差异。
A systematic study of the ozone potential energy surface was performed by means of high level ab initio techniques. The methods include icMR-CISD and icMR-AQCC with all electrons correlated using a full valence CAS reference space and basis sets up to sextuple-ζ quality along with extrapolation to the complete basis set limit. We computed a dense 3D grid as well as 1D cuts along stretching and bending coordinates around the open (C(2v)) equilibrium structure as well as along the minimum energy path to dissociation including the transition state and the van der Waals minimum region. The detailed analysis of our results confirms earlier calculations by the Schinke group and assures that these are not biased by deficiencies of the basis set, lack of relativistic corrections, or core correlation effects. Finally, we discuss possible sources of error that may explain the remaining discrepancies compared to experimental findings.