Variational quantum mechanical and active database approaches to the rotational-vibrational spectroscopy of ketene, H2CCO.
Variational quantum mechanical and active database approaches to the rotational-vibrational spectroscopy of ketene, H2CCO.
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乙烯酮、H2CCO 旋转振动光谱的变分量子力学和主动数据库方法。
DOI：
10.1063/1.3625404
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
A. Császár
中科院分区：
文献类型：
--
作者：
C. Fábri;E. Mátyus;T. Furtenbacher;L. Nemes;Béla Mihály;Tímea Zoltáni;A. Császár
本文提出了一种计算半刚性分子振转能级的变分量子力学方法，该方法采用Eckart-Watson哈密顿量的离散变量表示、完整的、“精确的”势能面以及振动子空间的选择.分子对称性是通过一个适应性强的Lanczos算法。除了对称性标签，零阶刚性转子和谐振子量子数被用来表征计算的振转态。利用所提出的计算分子光谱算法，计算并表征了乙烯酮的母体同位素H（2）（12）C=（12）C =（16）O的基态电子态的大量振转态，最高J = 50.在12篇参考文献的基础上，共收集到3982个H（2）（12）C=（12）C=（16）O的振转跃迁，其中3194个被确认。这些跃迁形成两个光谱网络（SN）。邻位和帕拉SN分别包含2489和705个经验证的跃迁以及1251和471个经验证的能级。计算出的能量水平与获得的能量水平进行比较，直到J = 41，通过反演协议的基础上收集验证测量的振转跃迁。准确的反转能级允许提出新的分配。阐明了烯酮振转光谱中的一些不规则性和不规则性。
A variational quantum mechanical protocol is presented for the computation of rovibrational energy levels of semirigid molecules using discrete variable representation of the Eckart-Watson Hamiltonian, a complete, "exact" inclusion of the potential energy surface, and selection of a vibrational subspace. Molecular symmetry is exploited via a symmetry-adapted Lanczos algorithm. Besides symmetry labels, zeroth-order rigid-rotor and harmonic-oscillator quantum numbers are employed to characterize the computed rovibrational states. Using the computational molecular spectroscopy algorithm presented, a large number of rovibrational states, up to J = 50, of the ground electronic state of the parent isotopologue of ketene, H(2) (12)C=(12)C=(16)O, were computed and characterized. Based on 12 references, altogether 3982 measured and assigned rovibrational transitions of H(2) (12)C=(12)C=(16)O have been collected, from which 3194 were validated. These transitions form two spectroscopic networks (SN). The ortho and the para SNs contain 2489 and 705 validated transitions and 1251 and 471 validated energy levels, respectively. The computed energy levels are compared with energy levels obtained, up to J = 41, via an inversion protocol based on this collection of validated measured rovibrational transitions. The accurate inverted energy levels allow new assignments to be proposed. Some regularities and irregularities in the rovibrational spectrum of ketene are elucidated.