Dwell Times, Wavepacket Dynamics, and Quantum Trajectories for Particles with Spin 1/2.

The theoretical connections between quantum trajectories and quantum dwell times, previously explored in the context of 1D time-independent stationary scattering applications, are here generalized for multidimensional time-dependent wavepacket applications for particles with spin 1/2. In addition to dwell times, trajectory-based dwell time distributions are also developed, and compared with previous distributions based on the dwell time operator and the flux-flux correlation function. Dwell time distributions are of interest, in part because they may be of experimental relevance. In addition to standard unipolar quantum trajectories, bipolar quantum trajectories are also considered, and found to relate more directly to the dwell time (and other quantum time) quantities of greatest relevance for scattering applications. Detailed calculations are performed for a benchmark 3D spin-1/2 particle application, considered previously in the context of computing quantum arrival times.

Matrix-free application of Hamiltonian operators in Coifman wavelet bases.

A means of evaluating the action of Hamiltonian operators on functions expanded in orthogonal compact support wavelet bases is developed, avoiding the direct construction and storage of operator matrices that complicate extension to coupled multidimensional quantum applications. Application of a potential energy operator is accomplished by simple multiplication of the two sets of expansion coefficients without any convolution. The errors of this coefficient product approximation are quantified and lead to use of particular generalized coiflet bases, derived here, that maximize the number of moment conditions satisfied by the scaling function. This is at the expense of the number of vanishing moments of the wavelet function (approximation order), which appears to be a disadvantage but is shown surmountable. In particular, application of the kinetic energy operator, which is accomplished through the use of one-dimensional (1D) [or at most two-dimensional (2D)] differentiation filters, then degrades in accuracy if the standard choice is made. However, it is determined that use of high-order finite-difference filters yields strongly reduced absolute errors. Eigensolvers that ordinarily use only matrix-vector multiplications, such as the Lanczos algorithm, can then be used with this more efficient procedure. Applications are made to anharmonic vibrational problems: a 1D Morse oscillator, a 2D model of proton transfer, and three-dimensional vibrations of nitrosyl chloride on a global potential energy surface.

Plasmonic enhancement of Raman optical activity in molecules near metal nanoshells.

Surface-enhanced Raman optical activity (SEROA) is investigated theoretically for molecules near a metal nanoshell. For this purpose, induced molecular electric dipole, magnetic dipole, and electric quadrupole moments must all be included. The incident field and the induced multipole fields all scatter from the nanoshell, and the scattered waves can be calculated via extended Mie theory. It is straightforward in this framework to calculate the incident frequency dependence of SEROA intensities, i.e., SEROA excitation profiles. The differential Raman scattering is examined in detail for a simple chiroptical model that provides analytical forms for the relevant dynamical molecular response tensors. This allows a detailed investigation into circumstances that simultaneously provide strong enhancement of differential intensities and remain selective for molecules with chirality.

Quantum and electromagnetic propagation with the conjugate symmetric Lanczos method.

The conjugate symmetric Lanczos (CSL) method is introduced for the solution of the time-dependent Schrodinger equation. This remarkably simple and efficient time-domain algorithm is a low-order polynomial expansion of the quantum propagator for time-independent Hamiltonians and derives from the time-reversal symmetry of the Schrodinger equation. The CSL algorithm gives forward solutions by simply complex conjugating backward polynomial expansion coefficients. Interestingly, the expansion coefficients are the same for each uniform time step, a fact that is only spoiled by basis incompleteness and finite precision. This is true for the Krylov basis and, with further investigation, is also found to be true for the Lanczos basis, important for efficient orthogonal projection-based algorithms. The CSL method errors roughly track those of the short iterative Lanczos method while requiring fewer matrix-vector products than the Chebyshev method. With the CSL method, only a few vectors need to be stored at a time, there is no need to estimate the Hamiltonian spectral range, and only matrix-vector and vector-vector products are required. Applications using localized wavelet bases are made to harmonic oscillator and anharmonic Morse oscillator systems as well as electrodynamic pulse propagation using the Hamiltonian form of Maxwell's equations. For gold with a Drude dielectric function, the latter is non-Hermitian, requiring consideration of corrections to the CSL algorithm.

Improving the accuracy of Weyl-Heisenberg wavelet and symmetrized Gaussian representations using customized phase-space-region operators.

A particular basis set method developed by one of the authors, involving maximally localized orthogonal Weyl-Heisenberg wavelets (or "weylets") and a phase space truncation scheme, has been successfully applied to exact quantum calculations for many degrees of freedom (DOF's) [B. Poirier and A. Salam, J. Chem. Phys. 121, 1740 (2004)]. However, limitations in accuracy arise in the many-DOF case, owing to memory limits on conventional computers. This paper addresses this accuracy limitation by introducing phase space region operators (PSRO's) that customize individual weylet basis functions for the problem of interest. The construction of the PSRO's is straightforward, and does not require a priori knowledge of the desired eigenstates. The PSRO, when applied to weylets, as well as to simple phase space Gaussian basis functions, exhibits remarkable improvements in accuracy, reducing computed eigenvalue errors by orders of magnitude. The method is applied to various model systems at varying DOF's.

Rovibrational spectroscopy calculations of neon dimer using a phase space truncated Weyl-Heisenberg wavelet basis.

In a series of earlier articles [B. Poirier J. Theor. Comput. Chem. 2, 65 (2003); B. Poirier and A. Salam J. Chem. Phys. 121, 1690 (2004); B. Poirier and A. Salam J. Chem. Phys. 121, 1740 (2004)], a new method was introduced for performing exact quantum dynamics calculations in a manner that formally defeats exponential scaling with system dimensionality. The method combines an optimally localized, orthogonal Weyl-Heisenberg wavelet basis set with a simple phase space truncation scheme, and has already been applied to model systems up to 17 degrees of freedom (DOF's). In this paper, the approach is applied for the first time to a real molecular system (neon dimer), necessitating the development of an efficient numerical scheme for representing arbitrary potential energy functions in the wavelet representation. All bound rovibrational energy levels of neon dimer are computed, using both one DOF radial coordinate calculations and a three DOF Cartesian coordinate calculation. Even at such low dimensionalities, the approach is found to be competitive with another state-of-the-art method applied to the same system [J. Montgomery and B. Poirier J. Chem. Phys. 119, 6609 (2003)].