Journal ArticleDOI
Multilayer formulation of the multiconfiguration time-dependent Hartree theory
Haobin Wang,Michael Thoss +1 more
TLDR
In this paper, a multilayer formulation of the multiconfiguration time-dependent Hartree (MCTDH) theory is presented, where the single-particle (SP) functions in the original MCTDH method are further expressed employing a timedependent multi-figurational expansion, and the Dirac-Frenkel variational principle is applied to optimally determine the equations of motion.Abstract:
A multilayer (ML) formulation of the multiconfiguration time-dependent Hartree (MCTDH) theory is presented. In this new approach, the single-particle (SP) functions in the original MCTDH method are further expressed employing a time-dependent multiconfigurational expansion. The Dirac–Frenkel variational principle is then applied to optimally determine the equations of motion. Following this strategy, the SP groups are built in several layers, where each top layer SP can contain many more Cartesian degrees of freedom than in the previous formulation of the MCTDH method. As a result, the ML-MCTDH method has the capability of treating substantially more physical degrees of freedom than the original MCTDH method, and thus significantly enhances the ability of carrying out quantum dynamical simulations for complex molecular systems. The efficiency of the new formulation is demonstrated by converged quantum dynamical simulations for systems with a few hundred to a thousand degrees of freedom.read more
Citations
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Theoretical Study of Photoinduced Electron-Transfer Processes in the Dye−Semiconductor System Alizarin−TiO2
TL;DR: In this paper, photo-induced electron-transfer processes in the dye−semiconductor system alizarin−TiO2 are studied based on a recently developed method, which uses first-principles electronic structure calculations to characterize the system and to parametrize a model Hamiltonian including electronic−vibrational coupling.
Journal ArticleDOI
Reaction dynamics with the multi-layer multi-configurational time-dependent Hartree approach: H + CH4 → H2 + CH3 rate constants for different potentials
Ralph Welsch,Uwe Manthe +1 more
TL;DR: The multi-layer extension of the multi-configurational time-dependent Hartree approach is applied to the investigation of elementary bimolecular chemical reactions and results indicate that an accurate description of all transition state frequencies is important to obtain accurate thermal rate constants.
Journal ArticleDOI
Multiconfigurational time-dependent Hartree calculations for tunneling splittings of vibrational states: Theoretical considerations and application to malonaldehyde
TL;DR: Studying the dependence of the tunneling splittings on the vibrational excitation, good agreement with available experimental results is found and intuitive interpretations of the results can be given.
Journal ArticleDOI
Resonances in the entrance channel of the elementary chemical reaction of fluorine and methane
Till Westermann,Jongjin B. Kim,Marissa L. Weichman,Christian Hock,Tara I. Yacovitch,Juliana Palma,Daniel M. Neumark,Uwe Manthe +7 more
TL;DR: A clear picture of resonances in the F+CH4 system is deduced from high-resolution slow electron velocity-map imaging (SEVI) spectra and accurate full-dimensional (12D) quantum dynamics simulations in the picosecond regime.
Journal ArticleDOI
Reduced density matrix hybrid approach: An efficient and accurate method for adiabatic and non-adiabatic quantum dynamics
TL;DR: In this paper, the authors present a new approach to calculate real-time quantum dynamics in complex systems based on the partitioning of a system's environment into core and reservoir modes with the former to be treated quantum mechanically and the latter classically.
References
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Journal ArticleDOI
Light-Induced Redox Reactions in Nanocrystalline Systems
Anders Hagfeldt,Michael Graetzel +1 more
TL;DR: A review with 156 refs on interfacial electron transfer reactions in colloidal semiconductor solns and thin films and their application for solar light energy conversion and photocatalytic water purifn is presented in this paper.
Journal ArticleDOI
Dynamics of the dissipative two-state system
Anthony J. Leggett,Sudip Chakravarty,Alan T. Dorsey,Matthew P. A. Fisher,Anupam Garg,Wilhelm Zwerger +5 more
TL;DR: In this article, a functional-integral approach to the dynamics of a two-state system coupled to a dissipative environment is presented, and an exact and general prescription for the reduction, under appropriate circumstances, of the problem of a system tunneling between two wells in the presence of dissipative environments to the spin-boson problem is given.
Book
Quantum Dissipative Systems
TL;DR: In this paper, the authors present a survey of the various approaches to Quantum-Statistical metastability, including Imaginary-Time and Real-Time Approaches Influence Functional Method Phenomenological and Microscopic System-Plus-Reservoir Models Linear and Nonlinear Quantum Environments Ohmic, Super-Ohmic, and Sub-ohmic Dissipation Quantum Decoherence and Relaxation Correlation Functions, Response Functions, and Fluctuation-Dissipation Theorem Damped Quantum Mechanical Harmonic Oscillator Quantum Brownian Motion Thermodynamic Variational
Journal ArticleDOI
The multiconfiguration time-dependent Hartree (MCTDH) method: a highly efficient algorithm for propagating wavepackets
TL;DR: In this article, a review of the multiconfiguration time-dependent Hartree (MCTDH) method for propagating wavepackets is given, and the formal derivation, numerical implementation, and performance of the method are detailed.
Journal ArticleDOI
Trajectory Surface Hopping Approach to Nonadiabatic Molecular Collisions: The Reaction of H+ with D2
John C. Tully,Richard K. Preston +1 more
TL;DR: In this article, an extension of the classical trajectory approach is proposed that may be useful in treating many types of nonadiabatic molecular collisions, where nuclei are assumed to move classically on a single potential energy surface until an avoided surface crossing or other region of large NDE coupling is reached.