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

Baeck, Kyoung Koo

doi:10.1002/qua.25088

Cited by 5 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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Practical approximation of the non-adiabatic coupling terms for same-symmetry interstate crossings by using adiabatic potential energies only

Baeck

2017

The Journal of Chemical Physics

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A very simple equation, F=[(∂(V-V)/∂Q)/(V-V)]/2, giving a reliable magnitude of non-adiabatic coupling terms (NACTs, F's) based on adiabatic potential energies only (V and V) was discovered, and its reliability was tested for several prototypes of same-symmetry interstate crossings in LiF, C, NHCl, and CHSH molecules. Our theoretical derivation starts from the analysis of the relationship between the Lorentzian dependence of NACTs along a diabatization coordinate and the well-established linear vibronic coupling scheme. This analysis results in a very simple equation, α=2κ/Δ, enabling the evaluation of the Lorentz function α parameter in terms of the coupling constant κ and the energy gap Δ (Δ=|V-V| ) between adiabatic states at the crossing point Q. Subsequently, it was shown that Q corresponds to the point where F exhibit maximum values if we set the coupling parameter as κ=[(V-V)⋅(∂(V-V)/∂Q)]/2. Finally, we conjectured that this relation could give reasonable values of NACTs not only at the crossing point but also at other geometries near Q. In this final approximation, the pre-defined crossing point Q is not required. The results of our test demonstrate that the approximation works much better than initially expected. The present new method does not depend on the selection of an ab initio method for adiabatic electronic states but is currently limited to local non-adiabatic regions where only two electronic states are dominantly involved within a nuclear degree of freedom.

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

Cited by 5 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

Practical approximation of the non-adiabatic coupling terms for same-symmetry interstate crossings by using adiabatic potential energies only

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