Issue 3, 2009

Quantum-mechanical wavepacket propagation in a sparse, adaptive basis of interpolating Gaussians with collocation

Abstract

We present an extension of our earlier work on adaptive quantum wavepacket dynamics [B. Hartke, Phys. Chem. Chem. Phys., 2006, 8, 3627]. In this dynamically pruned basis representation the wavepacket is only stored at places where it has non-negligible contributions. Here we enhance the former 1D proof-of-principle implementation to higher dimensions and optimize it by a new basis set, interpolating Gaussians with collocation. As a further improvement the TNUM approach from Lauvergnat and Nauts [J. Chem. Phys., 2002, 116, 8560] was implemented, which in combination with our adaptive representation offers the possibility of calculating the whole Hamiltonian on-the-fly. For a two-dimensional artificial benchmark and a three-dimensional real-life test case, we show that a sparse matrix implementation of this approach saves memory compared to traditional basis representations and comes even close to the efficiency of the fast Fourier transform method. Thus we arrive at a quantum wavepacket dynamics implementation featuring several important black-box characteristics: it can treat arbitrary systems without code changes, it calculates the kinetic and potential part of the Hamiltonian on-the-fly, and it employs a basis that is automatically optimized for the ongoing wavepacket dynamics.

Graphical abstract: Quantum-mechanical wavepacket propagation in a sparse, adaptive basis of interpolating Gaussians with collocation

Article information

Article type
Paper
Submitted
19 Aug 2008
Accepted
30 Sep 2008
First published
17 Nov 2008

Phys. Chem. Chem. Phys., 2009,11, 463-475

Quantum-mechanical wavepacket propagation in a sparse, adaptive basis of interpolating Gaussians with collocation

J. Sielk, H. F. von Horsten, F. Krüger, R. Schneider and B. Hartke, Phys. Chem. Chem. Phys., 2009, 11, 463 DOI: 10.1039/B814315C

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