Basics of the time‐dependent wave‐packet propagation for photodissociations of polyatomic systems

Baeck, Kyoung Koo

doi:10.1002/qua.25088

Cited by 7 publications

(2 citation statements)

References 64 publications

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“…In the past decades many problems in Physics and Chemistry have been thus addressed with WPP techniques (see e.g. [17][18][19][20][21][22][23][24][25][26] ).…”

Section: Introductionmentioning

confidence: 99%

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Ultrafast Dynamics of Electronic Resonances in Molecules Adsorbed on Metal Surfaces: A Wave Packet Propagation Approach

Aguilar-Galindo

Borisov

Díaz‐Tendero

2021

J. Chem. Theory Comput.

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We present a wave packet propagation-based method to study the electron dynamics in molecular species in the gas phase and adsorbed on metal surfaces. It is a very general method that can be employed to any system where the electron dynamics is dominated by an active electron and the coupling between the discrete and continuum electronic states is of importance. As an example one can consider resonant moleculesurface electron transfer or molecular photoionization. Our approach is based on a 1 computational strategy allowing to incorporate ab initio inputs from Quantum Chemistry methods, such as Density Functional Theory, Hartree-Fock and Coupled Cluster.Thus, the electronic structure of the molecule is fully taken into account. The electron wave function is represented on a 3D grid in spatial coordinates, and its temporal evolution is obtained from the solution of the time dependent Schrödinger equation. We illustrate our method with an example -electron dynamics of anionic states localized on organic molecules adsorbed on metal surfaces. In particular, we study resonant charge transfer from π * orbitals of three vinyl derivatives (acrylamide, acrylonitrile, and acrolein) adsorbed on a Cu(100) surface. Electron transfer between these lowest unoccupied molecular orbitals and the metal surface is extremely fast, leading to a decay of the population of the molecular anion on the femtosecond timescale. We detail how to analyze the time-dependent electronic wave function in order to obtain the relevant information on the system: the energies and lifetimes of the molecule-localized quasi-stationary states, their associated resonant wavefunctions, and the population decay channels. In particular, we demonstrate the effect of the electronic structure of the substrate on the energy and wave vector distribution of the hot electrons injected into the metal by the decaying molecular resonance.

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“…In the past decades many problems in Physics and Chemistry have been thus addressed with WPP techniques (see e.g. [17][18][19][20][21][22][23][24][25][26] ).…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, the WPP naturally allows considering quantum systems under the action of the explicitly time-dependent Hamiltonians as relevant for the attosecond science, − for example. In the past few decades, many problems in Physics and Chemistry have been thus addressed with WPP techniques (see e.g., refs − ).…”

Section: Introductionmentioning

confidence: 99%

Ultrafast Dynamics of Electronic Resonances in Molecules Adsorbed on Metal Surfaces: A Wave Packet Propagation Approach

Aguilar-Galindo

Borisov

Díaz‐Tendero

2021

J. Chem. Theory Comput.

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Theoretical chemistry in Korea: Professor Yoon Sup Lee and the early stages of theoretical chemistry in Korea

Lee¹,

Jung²

2016

Int J of Quantum Chemistry

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Fitting of Coupled Potential Energy Surfaces via Discovery of Companion Matrices by Machine Intelligence

Shu,

Varga,

Parameswaran

et al. 2024

J. Chem. Theory Comput.

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Fitting coupled potential energy surfaces is a critical step in simulating electronically nonadiabatic chemical reactions and energy transfer processes. Analytic representation of coupled potential energy surfaces enables one to perform detailed dynamics calculations. Traditionally, fitting is performed in a diabatic representation to avoid fitting the cuspidal ridges of coupled adiabatic potential energy surfaces at conical intersection seams. In this work, we provide an alternative approach by carrying out fitting in the adiabatic representation using a modified version of the Frobenius companion matrices, whose usage was first proposed by Opalka and Domcke. Their work involved minimizing the errors in fits of the characteristic polynomial coefficients (CPCs) and diagonalizing the resulting companion matrix, whose eigenvalues are adiabatic potential energies. We show, however, that this may lead to complex eigenvalues and spurious discontinuities. To alleviate this problem, we provide a new procedure for the automatic discovery of CPCs and the diagonalization of a companion matrix by using a special neural network architecture. The method effectively allows analytic representation of global coupled adiabatic potential energy surfaces and their gradients with only adiabatic energy input and without experience-based selection of a diabatization scheme. We demonstrate that the new procedure, called the companion matrix neural network (CMNN), is successful by showing applications to LiH, H3, phenol, and thiophenol.

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Basics of the time‐dependent wave‐packet propagation for photodissociations of polyatomic systems

Cited by 7 publications

References 64 publications

Ultrafast Dynamics of Electronic Resonances in Molecules Adsorbed on Metal Surfaces: A Wave Packet Propagation Approach

Ultrafast Dynamics of Electronic Resonances in Molecules Adsorbed on Metal Surfaces: A Wave Packet Propagation Approach

Theoretical chemistry in Korea: Professor Yoon Sup Lee and the early stages of theoretical chemistry in Korea

Fitting of Coupled Potential Energy Surfaces via Discovery of Companion Matrices by Machine Intelligence

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