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首页> 外文期刊>The Journal of Chemical Physics >Full-dimensional (15-dimensional) quantum-dynamical simulation of the protonated water dimer.I.Hamiltonian setup and analysis of the ground vibrational state
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Full-dimensional (15-dimensional) quantum-dynamical simulation of the protonated water dimer.I.Hamiltonian setup and analysis of the ground vibrational state

机译：质子化水二聚体的全尺寸（15维）量子动力学模拟I.哈密顿量和地面振动状态的分析

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Quantum-dynamical full-dimensional (15D) calculations are reported for the protonated water dimer (HsO_2~+) using the multiconfiguration time-dependent Hartree (MCTDH) method.The dynamics is described by curvilinear coordinates.The expression of the kinetic energy operator in this set of coordinates is given and its derivation,following the polyspherical method,is discussed.The potential-energy surface (PES) employed is that of Huang et al.[J.Chem.Phys.122,044308 (2005)].A scheme for the representation of the PES is discussed which is based on a high-dimensional model representation scheme,but modified to take advantage of the mode-combination representation of the vibrational wave function used in MCTDH.The convergence of the PES expansion used is quantified and evidence is provided that it correctly reproduces the reference PES at least for the range of energies of interest.The reported zero point energy of the system is converged with respect to the MCTDH expansion and in excellent agreement (16.7 cm~(-1) below) with the diffusion Monte Carlo result on the PES of Huang et al.The highly fluxional nature of the cation is accounted for through use of curvilinear coordinates.The system is found to interconvert between equivalent minima through wagging and internal rotation motions already when in the ground vibrational state,i.e.,T=0.It is shown that a converged quantum-dynamical description of such a flexible,multiminima system is possible.
机译：报道了使用多构型时变哈特里（MCTDH）方法对质子化水二聚体（HsO_2〜+）进行量子动力学全维（15D）计算，其动力学用曲线坐标表示。给出了这套坐标，并按照多球法讨论了它的推导。所用的势能表面（PES）是Huang等人的[J.Chem.Phys.122,044308（2005）]。讨论了基于高维模型表示方案的PES表示方案，但对它进行了修改以利用MCTDH中使用的振动波函数的模式组合表示。量化了PES展开的收敛性并且提供的证据表明，至少在感兴趣的能量范围内，它可以正确地重现参考PES。报告的系统零点能量在MCTDH扩展方面收敛，并且具有出色的性能。与Huang等人的PES上的扩散蒙特卡罗结果一致（16.7 cm〜（-1））。阳离子的高通量性质是通过使用曲线坐标来说明的。发现该系统在等效极小值之间相互转换处于地面振动状态（即T = 0）时已经通过摆动和内部旋转运动进行了研究。结果表明，这种灵活的多极小系统的收敛的量子动力学描述是可能的。

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