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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Simultaneous Evaluation of Multiple Rotationally Excited States of H_3~+, H_3O~+, and CH_5~+ Using Diffusion Monte Carlo
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Simultaneous Evaluation of Multiple Rotationally Excited States of H_3~+, H_3O~+, and CH_5~+ Using Diffusion Monte Carlo

机译：使用扩散蒙特卡洛同时评估H_3〜+，H_3O〜+和CH_5〜+的多个旋转激发态

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摘要

An extension to diffusion Monte Carlo (DMC) is proposed for simultaneous evaluation of multiple rotationally excited states of fluxional molecules. The method employs an expansion of the rotational dependence of the wave function in terms of the eigenstates of the symmetric top Hamiltonian. Within this DMC approach, each walker has a separate rotational state vector for each rotational state of interest. The values of the coefficients in the expansion of the rotational state vector associated with each walker, as well as the locations of the walkers, evolve in imaginary time under the action of a propagator based on the imaginary-time time-dependent Schr?dinger equation. The approach is first applied to H_3~+, H_2D~+, and H_3O~+ for which the calculated energies can be compared to benchmark values. For low to moderate values of J the DMC results are found to be accurate to within the evaluated statistical uncertainty. The rotational dependence of the vibrational part of the wave function is also investigated, and significant rotation?vibration interaction is observed. Based on the successful application of this approach to H_3~+, H_2D~+, and H_3O~+, the method was applied to calculations of the rotational energies and wave functions for CH_5~+ with v = 0 and J ≤ 10. Based on these calculations, the rotational energy progression is shown to be consistent with that for a nearly spherical top molecule, and little evidence of rotation?vibration interaction is found in the vibrational wave function.
机译：提出了扩散蒙特卡罗（DMC）的扩展，用于同时评估通量分子的多个旋转激发态。该方法根据对称顶部哈密顿量的本征态扩展了波函数的旋转相关性。在这种DMC方法中，每个助行器都有一个针对每个感兴趣旋转状态的独立旋转状态向量。与每个助行器相关联的旋转状态向量的扩展系数值以及助行器的位置，在传播器的作用下，基于虚时随时间的薛定er方程在虚时中演化。 。该方法首先应用于H_3〜+，H_2D〜+和H_3O〜+，可以将计算出的能量与基准值进行比较。对于J的中低值，发现DMC结果在评估的统计不确定性范围内是准确的。还研究了波函数振动部分的旋转依赖性，并观察到了显着的旋转振动相互作用。在此方法成功应用于H_3〜+，H_2D〜+和H_3O〜+的基础上，将该方法应用于计算v = 0且J≤10的CH_5〜+的旋转能和波函数。这些计算表明，旋转能级数与近似球形的顶部分子是一致的，在振动波函数中很少发现旋转-振动相互作用的证据。

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