Theoretical description of charge migration with a single Slater-determinant and beyond

Kuleff, Alexander I.; Dreuw, Andreas

doi:10.1063/1.3058899

Cited by 23 publications

(23 citation statements)

References 31 publications

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“…Whenever the excess charge is localized on a few atoms in a fragment, the approximation of preserved frontier orbitals may become problematic; then, a third-order expansion may account, for example, for the spatial expansion of the electron density in small anions with respect to the neutral molecules, as discussed for SCC-DFTB recently [48]. Also, it was shown that, after removing an electron from the HOMO, this orbital remains static and the charge migration is driven by lower lying orbitals [49]. We have tested this approximation for the nucleobase guanine, which is the dominant hole-carrying fragment in DNA.…”

Section: The Koopmans Theorem and The Zeroth-order Termmentioning

confidence: 99%

A hybrid approach to simulation of electron transfer in complex molecular systems

Kubař

Elstner

2013

J. R. Soc. Interface.

130

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Electron transfer (ET) reactions in biomolecular systems represent an important class of processes at the interface of physics, chemistry and biology. The theoretical description of these reactions constitutes a huge challenge because extensive systems require a quantum-mechanical treatment and a broad range of time scales are involved. Thus, only small model systems may be investigated with the modern density functional theory techniques combined with non-adiabatic dynamics algorithms. On the other hand, model calculations based on Marcus's seminal theory describe the ET involving several assumptions that may not always be met. We review a multi-scale method that combines a non-adiabatic propagation scheme and a linear scaling quantum-chemical method with a molecular mechanics force field in such a way that an unbiased description of the dynamics of excess electron is achieved and the number of degrees of freedom is reduced effectively at the same time. ET reactions taking nanoseconds in systems with hundreds of quantum atoms can be simulated, bridging the gap between non-adiabatic ab initio simulations and model approaches such as the Marcus theory. A major recent application is hole transfer in DNA, which represents an archetypal ET reaction in a polarizable medium. Ongoing work focuses on hole transfer in proteins, peptides and organic semi-conductors.

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Section: The Koopmans Theorem and The Zeroth-order Termmentioning

confidence: 99%

A hybrid approach to simulation of electron transfer in complex molecular systems

Kubař

Elstner

2013

J. R. Soc. Interface.

130

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“…10 We note that using cDFT to create the initial state largely removes this problem, and makes charge migration dynamics possible.…”

Section: Discussionmentioning

confidence: 99%

The influence of initial conditions on charge transfer dynamics

Eshuis

Voorhis

2009

Phys. Chem. Chem. Phys.

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In this work we address the influence of the initial state on electron transfer dynamics by comparing two different ways of setting up the initial state, namely by taking an electron from the HOMO of a DFT ground state, or by using constrained DFT to self-consistently create the initial state. We solve the TDKS equations for the benzyl-pentafluorobenzene cation. The neutral molecule has a localised HOMO, which gives a natural partitioning in donor and acceptor group. We compare the electronic dynamics for varying angle between donor and acceptor and for varying basis set. We show that the methods lead to essentially equivalent results, but that the use of cDFT gives higher currents and a more consistent initial state with respect to variation of basis set and geometry.

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“…After removing an electron due to sudden ionization of molecules by extreme ultraviolet (XUV) light, a hole is created which could be oscillating along different molecule sites. A purely electronic motion that takes place in its intrinsic time scale, few “fs” to “as,” is called charge (hole) migration, whereas the subsequent time evolution of molecule, from femto to pico seconds, including nuclear motion is designated as charge transfer [2, 3, 10, 11, 13–27]. Indeed, Charge migration analysis could be particularly important in governing early electronic dynamics, subsequent charge transfer [17] and photo‐induced chemical reactions.…”

Section: Introductionmentioning

confidence: 99%

Charge migration in caffeine: A real‐time time‐dependent density functional theory study

Khalili

Vafaee

Cho

et al. 2021

Int J of Quantum Chemistry

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We present a real‐time time dependent density functional theory approach to simulate charge migration of caffeine molecule after selective photoionization. According to the fact that the time evolution of the created hole can affect the molecular reaction and subsequent dynamics difference from its original structure, we studied the dominant frequency variation of caffeine charge oscillation after ionization of outer shell orbital. In this work, we determined the main orbitals participating in the total charge migration process by comparing the dipole moment peaks to the Fourier signals of the time dependent molecular orbitals (MOs) occupation. Having used the Bader charge analysis, we showed that different valence ionization of molecule resulted in a distinct charge migration between different regions, functional groups, and atoms of cations. We represented two interesting different cases: 1‐for ionization out from 46th MO of caffeine, the MOs interfere of the cation resulted in a charge migration between oxygen atoms and upper nitrogen of five‐membered ring, 2‐ for ionization out from 39th MO of caffeine, a different behavior of hole occurred according to which the hole spread throughout the whole molecule. Therefore, a specific MO ionization could result in a dramatically different migration and active site of cation.

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Theoretical description of charge migration with a single Slater-determinant and beyond

Cited by 23 publications

References 31 publications

A hybrid approach to simulation of electron transfer in complex molecular systems

A hybrid approach to simulation of electron transfer in complex molecular systems

The influence of initial conditions on charge transfer dynamics

Charge migration in caffeine: A real‐time time‐dependent density functional theory study

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