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Quantum-dynamical full-dimensional (15D) calculations are reported for theprotonated water dimer (H5O2+) using the multiconfiguration time-dependentHartree (MCTDH) method. The dynamics is described by curvilinear coordinates.The expression of the kinetic energy operator in this set of coordinates isgiven and its derivation, following the polyspherical method, is discussed. ThePES employed is that of Huang et al. [JCP, 122, 044308, (2005)]. A scheme forthe representation of the potential energy surface (PES) is discussed which isbased on a high dimensional model representation scheme (cut-HDMR), butmodified to take advantage of the mode-combination representation of thevibrational wavefunction used in MCTDH. The convergence of the PES expansionused is quantified and evidence is provided that it correctly reproduces thereference PES at least for the range of energies of interest. The reported zeropoint energy of the system is converged with respect to the MCTDH expansion andin excellent agreement (16.7 cm-1 below) with the diffusion Monte Carlo resulton the PES of Huang et al. The highly fluxional nature of the cation isaccounted for through use of curvilinear coordinates. The system is found tointerconvert between equivalent minima through wagging and internal rotationmotions already when in the ground vibrational-state, i.e., T=0. It is shownthat a converged quantum-dynamical description of such a flexible, multi-minimasystem is possible.

Full dimensional (15D) quantum-dynamical simulation of the protonated water-dimer I: Hamiltonian setup and analysis of the ground vibrational state