Vibrational Density Matrix Renormalization Group

Variational approaches for the calculation of vibrational wave functions and energies are a natural route to obtain highly accurate results with controllable errors. However, the unfavorable scaling and the resulting high computational cost of standard variational approaches limit their application to small molecules with only few vibrational modes. Here, we demonstrate how the density matrix renormalization group (DMRG) can be exploited to optimize vibrational wave functions (vDMRG) expressed as matrix product states. We study the convergence of these calculations with respect to the size of the local basis of each mode, the number of renormalized block states, and the number of DMRG sweeps required. We demonstrate the high accuracy achieved by vDMRG for small molecules that were intensively studied in the literature. We then proceed to show that the complete fingerprint region of the sarcosyn-glycin dipeptide can be calculated with vDMRG.Comment: 21 pages, 5 figures, 4 table

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

Semiclassical statistico-dynamical description of polyatomic photo-dissociations: State-resolved distributions

An alternative methodology to investigate indirect polyatomic processes with quasi-classical trajectories is proposed, which effectively avoids any binning or weighting procedure while provides rovibrational resolution. Initial classical states are started in terms of angle-action variables to closely match the quantum experimental conditions and later transformed into Cartesian coordinates, following an algorithm very recently published [J. Chem. Phys. 130, 114103 (2009)]. Trajectories are then propagated using the 'association' picture, i.e. an inverse dynamics simulation in the spirit of the exit-channel corrected phase space theory of Hamilton and Brumer [J. Chem. Phys. 82, 595 (1985)], which is shown to be particularly convenient. Finally, an approximate quasi-classical formula is provided which under general conditions can be used to add possible rotational structures into the vibrationally-resolved quasi-classical distributions. To introduce the method and illustrate its capabilities, correlated translational energy distributions from recent experiments in the photo-dissociation of ketene at 308 nm [J. Chem. Phys. 124, 014303 (2006)] are investigated. Quite generally, the overall theoretical algorithm reduces the total number of trajectories to integrate and allows for fully theoretical predictions of experiments on polyatomics.Comment: 10 pages, 3 figures, submitted to Phys. Chem. Chem. Phys; v2: corrects Fig. 3 and its discussio

Nonlinear model identification and spectral submanifolds for multi-degree-of-freedom mechanical vibrations

In a nonlinear oscillatory system, spectral submanifolds (SSMs) are the smoothest invariant manifolds tangent to linear modal subspaces of an equilibrium. Amplitude-frequency plots of the dynamics on SSMs provide the classic backbone curves sought in experimental nonlinear model identification. We develop here a methodology to compute analytically both the shape of SSMs and their corresponding backbone curves from a data-assimilating model fitted to experimental vibration signals. Using examples of both synthetic and real experimental data, we demonstrate that this approach reproduces backbone curves with high accuracy.Comment: 32 pages, 4 figure

Evidence for a gravitational Myers effect

An indication for the existence of a collective Myers solution in the non-abelian D0-brane Born-Infeld action is the presence of a tachyonic mode in fluctuations around the standard diagonal background. We show that this computation for non-abelian D0-branes in curved space has the geometric interpretation of computing the eigenvalues of the geodesic deviation operator for U(N)-valued coordinates. On general grounds one therefore expects a geometric Myers effect in regions of sufficiently negative curvature. We confirm this by explicit computations for non-abelian D0-branes on a sphere and a hyperboloid. For the former the diagonal solution is stable, but not so for the latter. We conclude by showing that near the horizon of a Schwarzschild black hole one also finds a tachyonic mode in the fluctuation spectrum, signaling the possibility of a near-horizon gravitationally induced Myers effect.Comment: LaTeX, 23 page