Gaussian wavepacket dynamics has proven to be a useful semiclassical approximation for quantum simulations of high-dimensional systems with low anharmonicity. Compared to Heller's original local harmonic method, the variational Gaussian wavepacket dynamics is more accurate, but much more difficult to apply in practice because it requires evaluating the expectation values of the potential energy, gradient, and Hessian. If the variational approach is applied to the local cubic approximation of the potential, these expectation values can be evaluated analytically, but they still require the costly third derivative of the potential. To reduce the cost of the resulting local cubic variational Gaussian wavepacket dynamics, we describe efficient high-order geometric integrators, which are symplectic, time-reversible, and norm-conserving. For small time steps, they also conserve the effective energy. We demonstrate the efficiency and geometric properties of these integrators numerically on a multidimensional, nonseparable coupled Morse potential.
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http://dx.doi.org/10.1063/5.0180070 | DOI Listing |
J Phys Chem A
October 2024
OTI Lumionics Inc., 3415 American Drive Unit 1, Mississauga, Ontario L4V 1T4, Canada.
A method for performing variable-width (thawed) Gaussian wavepacket (GWP) variational dynamics on machine-learned potentials is presented. Instead of fitting the potential energy surface (PES), the anharmonic correction to the global harmonic approximation (GHA) is fitted using kernel ridge regression─this is a Δ-machine learning approach. The training set consists of energy differences between ab initio electronic energies and values given by the GHA.
View Article and Find Full Text PDFJ Chem Phys
September 2024
Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
In single vibronic level (SVL) fluorescence experiments, the electronically excited initial state is also excited in one or several vibrational modes. Because computing such spectra by evaluating all contributing Franck-Condon factors becomes impractical (and unnecessary) in large systems, here we propose a time-dependent approach based on Hagedorn wavepacket dynamics. We use Hagedorn functions-products of a Gaussian and carefully generated polynomials-to represent SVL initial states because in systems whose potential is at most quadratic, Hagedorn functions are exact solutions to the time-dependent Schrödinger equation and can be propagated with the same equations of motion as a simple Gaussian wavepacket.
View Article and Find Full Text PDFSci Rep
September 2024
School of Science, Jiangnan University, Wuxi, 214122, China.
The non-Hermitian skin effect and nonreciprocal behavior are sensitive to the boundary conditions, which are unique features of non-Hermitian systems. In such systems, eigenenergies can become complex, and all eigenstates tend to localize at the boundary, a phenomenon that contrasts with Hermitian topologies. In this work, we theoretically study the dynamic behavior of the propagation of Gaussian wavepackets inside a non-Hermitian lattice and analyze the self-acceleration process of bulk state or Gaussian wavepackets toward the system's boundary.
View Article and Find Full Text PDFNat Commun
June 2024
School of Optical-Electrical and Computer Engineering, University of Shanghai for Science and Technology, Shanghai, China.
J Phys Chem A
July 2024
Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, White City Campus, 80 Wood Lane, W12 0BZ London, U.K.
We report a protocol for the implementation of "reaction path following" from a transition state through a conical intersection, including both the path curvature induced by the derivative coupling and the corresponding induced electronic coherences. This protocol focuses on the "central" Gaussian wavepacket (initially unexcited) in the quantum Ehrenfest (QuEh) method. Like the reaction path following, the normal mode corresponding to the imaginary frequency at the transition state is given an initial momentum.
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