Force-field calculation and geometry of the HOOO radical.
Force-field calculation and geometry of the HOOO radical.
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DOI：
10.1063/1.4819323
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发表时间：
2013-09
期刊：
影响因子：
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通讯作者：
K. Suma;Y. Sumiyoshi;Y. Endo
中科院分区：
文献类型：
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作者：
K. Suma;Y. Sumiyoshi;Y. Endo
高级从头计算使用戴维森校正的多参考组态相互作用（MRCI）理论水平与Dunning的相关一致的基组和力场计算进行HOOO自由基。由力场计算得到的简谐振动频率和非简谐常数与红外-紫外实验振动频率的误差小于19 cm（-1）。由力场计算的振转相互作用常数得到的基态转动常数与实验测得的转动常数的误差小于0.9%，表明本文的量子化学计算和得到的光谱常数具有很高的精度.从实验确定的旋转常数结合理论推导的振动-旋转相互作用常数的平衡结构确定。所确定的几何参数与本MRCI计算的结果吻合得很好。
High-level ab initio calculations using the Davidson-corrected multireference configuration interaction (MRCI) level of theory with Dunning's correlation consistent basis sets and force-field calculations were performed for the HOOO radical. The harmonic vibrational frequencies and their anharmonic constants obtained by the force-field calculations reproduce the IR-UV experimental vibrational frequencies with errors less than 19 cm(-1). The rotational constants for the ground vibrational state obtained using the vibration-rotation interaction constants of the force-field calculations also reproduce the experimentally determined rotational constants with errors less than 0.9%, indicating that the present quantum chemical calculations and the derived spectroscopic constants have high accuracy. The equilibrium structure was determined from the experimentally determined rotational constants combined with the theoretically derived vibration-rotation interaction constants. The determined geometrical parameters agree well with the results of the present MRCI calculation.