Full dimensional (15D) quantum-dynamical simulation of the protonated water-dimer II: infrared spectrum and vibrational dynamics

The infrared absorption spectrum of the protonated water dimer (H5O2+) is simulated in full dimensionality (15D) in the spectral range 0-4000 cm-1. The calculations are performed using the Multiconfiguration Time-Dependent Hartree (MCTDH) method for propagation of wavepackets. All the fundamentals and several overtones of the vibrational motion are computed. The spectrum of H5O2+ is shaped to a large extent by couplings of the proton-transfer motion to large amplitude fluxional motions of the water molecules, water bending and water-water stretch motions. These couplings are identified and discussed, and the corresponding spectral lines assigned. The large couplings featured by H5O2+ do not hinder, however, to describe the coupled vibrational motion by well defined simple types of vibration (stretching, bending, etc.) based on well defined modes of vibration, in terms of which the spectral lines are assigned. Comparison of our results to recent experiments and calculations on the system is given. The reported MCTDH IR-spectrum is in very good agreement to the recently measured spectrum by Hammer et al. [JCP, 122, 244301, (2005)].Comment: 30 pages, 6 figures, submitted to J. Chem. Phy

Correlations in Ultracold Trapped Few-Boson Systems: Transition from Condensation to Fermionization

We study the correlation properties of the ground states of few ultracold bosons, trapped in double wells of varying barrier height in one dimension. Extending previous results on the signature of the transition from a Bose-condensed state via fragmentation to the hard-core limit, we provide a deeper understanding of that transition by relating it to the loss of coherence in the one-body density matrix and to the emerging long-range tail in the momentum spectrum. These are accounted for in detail by discussing the natural orbitals and their occupations. Our discussion is complemented by an analysis of the two-body correlation function.Comment: 22 pages, 7 figure

Excitations of Few-Boson Systems in 1-D Harmonic and Double Wells

We examine the lowest excitations of one-dimensional few-boson systems trapped in double wells of variable barrier height. Based on a numerically exact multi-configurational method, we follow the whole pathway from the non-interacting to the fermionization limit. It is shown how, in a purely harmonic trap, the initially equidistant, degenerate levels are split up due to interactions, but merge again for strong enough coupling. In a double well, the low-lying spectrum is largely rearranged in the course of fermionization, exhibiting level adhesion and (anti-)crossings. The evolution of the underlying states is explained in analogy to the ground-state behavior. Our discussion is complemented by illuminating the crossover from a single to a double well.Comment: 11 pages, 10 figure

Tunneling dynamics of few bosons in a double well

We study few-boson tunneling in a one-dimensional double well. As we pass from weak interactions to the fermionization limit, the Rabi oscillations first give way to highly delayed pair tunneling (for medium coupling), whereas for very strong correlations multi-band Rabi oscillations emerge. All this is explained on the basis of the exact few-body spectrum and without recourse to the conventional two-mode approximation. Two-body correlations are found essential to the understanding of the different tunnel mechanisms. The investigation is complemented by discussing the effect of skewing the double well, which offers the possibility to access specific tunnel resonancesComment: 10 pages, 8 figure

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

Quantum-dynamical full-dimensional (15D) calculations are reported for the protonated water dimer (H5O2+) 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 PES employed is that of Huang et al. [JCP, 122, 044308, (2005)]. A scheme for the representation of the potential energy surface (PES) is discussed which is based on a high dimensional model representation scheme (cut-HDMR), but modified to take advantage of the mode-combination representation of the vibrational wavefunction 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, multi-minima system is possible.Comment: 46 pages, 5 figures, submitted to J. Chem. Phy

Quantum dynamics of two bosons in an anharmonic trap: Collective vs internal excitations

This work deals with the effects of an anharmonic trap on an interacting two-boson system in one dimension. Our primary focus is on the role of the induced coupling between the center of mass and the relative motion as both anharmonicity and the (repulsive) interaction strength are varied. The ground state reveals a strong localization in the relative coordinate, counteracting the tendency to fragment for stronger repulsion. To explore the quantum dynamics, we study the system's response upon (i) exciting the harmonic ground state by continuously switching on an additional anharmonicity, and (ii) displacing the center of mass, this way triggering collective oscillations. The interplay between collective and internal dynamics materializes in the collapse of oscillations, which are explained in terms of few-mode models.Comment: 8 pages, 7 figure

Ultracold Few-Boson Systems in a Double-Well Trap

We investigate the transition of a quasi-one-dimensional few-boson system from a weakly correlated to a fragmented and finally a fermionized ground state. Our numerically exact analysis, based on a multi-configurational method, explores the interplay between different shapes of external and inter-particle forces. Specifically, we demonstrate that the addition of a central barrier to an otherwise harmonic trap may supports the system's fragmentation, with a symmetry-induced distinction between even and odd atom numbers. Moreover, the impact of inhomogeneous interactions is studied, where the effective coupling strength is spatially modulated. It is laid out how the ground state can be displaced in a controlled way depending on the trap and the degree of modulation. We present the one- and two-body densities and, beyond that, highlight the role of correlations on the basis of the natural occupations

The coupling of the hydrated proton to its first solvation shell

The transfer of a hydrated proton between water molecules in aqueous solution is accompanied by the large-scale structural reorganization of the environment as the proton relocates, giving rise to the Grotthus mechanism. The Zundel (H5O2+) and Eigen (H9O4+) cations are the main intermediate structures in this process. They exhibit radically different gas-phase infrared (IR) spectra, indicating fundamentally different environments of the solvated proton in its first solvation shell. The question arises: is there a least common denominator structure that explains the IR spectra of the Zundel and Eigen cations, and hence of the solvated proton? Full dimensional quantum simulations of these protonated cations demonstrate that two dynamical water molecules embedded in the static environment of the parent Eigen cation constitute this fundamental subunit. It is sufficient to explain the spectral signatures and anharmonic couplings of the solvated proton in its first solvation shell. In particular, we identify the anharmonic vibrational modes that explain the large broadening of the proton transfer peak in the experimental IR spectrum of the Eigen cation, of which the origin remained so far unclear. Our findings about the quantum mechanical structure of the first solvation shell provide a starting point for further investigations of the larger protonated water clusters with second and additional solvation shells.Comment: main article with 4 figures, methods, and supporting informatio

Composite fermionization of 1-D Bose-Bose mixtures

We study the ground states of one-dimensional Bose-Bose mixtures under harmonic confinement. As we vary the inter-species coupling strength up to the limit of infinite repulsion, we observe a generalized, composite-fermionization crossover. The initially coexisting phases demix as a whole (for weak intra-species interactions) and separate on an atomic level (for strong intra-species repulsion). By symmetry, the two components end up with strongly overlapping profiles, albeit sensitive to symmetry-breaking perturbations. Different pathways emerge in case the two components have different atom numbers, different intra-species interactions, or different masses and/or trap frequencies.Comment: 9 pages, 9 figure