Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions

Ramos, Pablo; Papadakis, Markos M.; Pavanello, Michele

doi:10.1021/jp511275e

Cited by 59 publications

(89 citation statements)

References 120 publications

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“…In addition, the problem of the electron delocalisation error in DFT electronic structure calculation of adiabatic electronic states is largely suppressed. Several DFT methods are available that yield diabatic electronic states, e.g., constrained DFT, [25][26][27][28][29] frozen density embedding, 30,31 and DFTB. [13][14][15] In the context of FSSH, a drawback of diabatic states is that all energies and nuclear gradients need to be transformed to the adiabatic representation as the nuclear dynamics should be run on the adiabatic states in this method.…”

Section: Introductionmentioning

confidence: 99%

Detailed balance, internal consistency, and energy conservation in fragment orbital-based surface hopping

Carof

Giannini

Blumberger

2017

The Journal of Chemical Physics

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We have recently introduced an efficient semi-empirical non-adiabatic molecular dynamics method for the simulation of charge transfer/transport in molecules and molecular materials, denoted fragment orbital-based surface hopping (FOB-SH) [J. Spencer et al., J. Chem. Phys. 145, 064102 (2016)]. In this method, the charge carrier wavefunction is expanded in a set of charge localized, diabatic electronic states and propagated in the time-dependent potential due to classical nuclear motion. Here we derive and implement an exact expression for the non-adiabatic coupling vectors between the adiabatic electronic states in terms of nuclear gradients of the diabatic electronic states. With the non-adiabatic coupling vectors (NACVs) available, we investigate how different flavours of fewest switches surface hopping affect detailed balance, internal consistency, and total energy conservation for electron hole transfer in a molecular dimer with two electronic states. We find that FOB-SH satisfies detailed balance across a wide range of diabatic electronic coupling strengths provided that the velocities are adjusted along the direction of the NACV to satisfy total energy conservation upon a surface hop. This criterion produces the right fraction of energy-forbidden (frustrated) hops, which is essential for correct population of excited states, especially when diabatic couplings are on the order of the thermal energy or larger, as in organic semiconductors and DNA. Furthermore, we find that FOB-SH is internally consistent, that is, the electronic surface population matches the average quantum amplitudes, but only in the limit of small diabatic couplings. For large diabatic couplings, inconsistencies are observed as the decrease in excited state population due to frustrated hops is not matched by a corresponding decrease in quantum amplitudes. The derivation provided here for the NACV should be generally applicable to any electronic structure approach where the electronic Hamiltonian is constructed in a diabatic electronic state basis.

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Section: Introductionmentioning

confidence: 99%

Detailed balance, internal consistency, and energy conservation in fragment orbital-based surface hopping

Carof

Giannini

Blumberger

2017

The Journal of Chemical Physics

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“…This framework has recently been applied [130,131] with great success to systems of biological interest and realistic size (such as portions of the DNA double helix), yielding qualitative and quantitative agreement with experimental data.…”

Section: Note On Self-interactionmentioning

confidence: 92%

“…The subsystem DFT method has been exploited to constrain spin and excess electron densities on specific fragments [127][128][129][130][131] even when KS-DFT fails to do so due to self-interaction error. This behavior of FDE arises from the fact that the FDE theory does not impose orthogonality between the orbitals of different subsystems, thus the typical delocalization of the KS orbitals originating from the orbital's hybridization is completely avoided.…”

Section: Note On Self-interactionmentioning

confidence: 99%

Subsystem density-functional theory as an effective tool for modeling ground and excited states, their dynamics and many-body interactions

Krishtal

Sinha

Genova

et al. 2015

J. Phys.: Condens. Matter

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113

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Subsystem Density-Functional Theory (DFT) is an emerging technique for calculating the electronic structure of complex molecular and condensed phase systems. In this topical review, we focus on some recent advances in this field related to the computation of condensed phase systems, their excited states, and the evaluation of many-body interactions between the subsystems. As subsystem DFT is in principle an exact theory, any advance in this field can have a dual role. One is the possible applicability of a resulting method in practical calculations. The other is the possibility of shedding light on some quantummechanical phenomenon which is more easily treated by subdividing a supersystem into subsystems. An example of the latter is many-body interactions. In the discussion, we present some recent work from our research group as well as some new results, casting them in the current state-of-the-art in this review as comprehensively as possible.2

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“…In addition, there are several extensions which require to combine results from different subsystem calculations in special ways. Examples are the calculation of excitonically coupled excitations or response properties, where time‐dependent DFT (TDDFT) results for embedded subsystems need to be combined, or pragmatic, physically motivated computational protocols for the description of quasi‐diabatic states as in calculations of transfer integrals in charge transport …”

Section: Introductionmentioning

confidence: 99%

“…Examples are the calculation of excitonically coupled excitations [28,29,[38][39][40] or response properties, [41] where timedependent DFT (TDDFT) results for embedded subsystems need to be combined, or pragmatic, physically motivated computational protocols for the description of quasi-diabatic states as in calculations of transfer integrals in charge transport. [42][43][44] On the one hand, this multitude of options offers great possibilities for a potential user in tailor-made descriptions of molecular processes; in fact, there are probably many interesting extensions that one could easily think of. On the other hand, the large number of variants of approximate FDE/sDFT computations may create confusion among non-expert users.…”

Section: Introductionmentioning

confidence: 99%

Serenity: A subsystem quantum chemistry program

et al. 2018

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We present the new quantum chemistry program Serenity. It implements a wide variety of functionalities with a focus on subsystem methodology. The modular code structure in combination with publicly available external tools and particular design concepts ensures extensibility and robustness with a focus on the needs of a subsystem program. Several important features of the program are exemplified with sample calculations with subsystem density-functional theory, potential reconstruction techniques, a projection-based embedding approach and combinations thereof with geometry optimization, semi-numerical frequency calculations and linear-response time-dependent density-functional theory. © 2018 Wiley Periodicals, Inc.

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Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions

Cited by 59 publications

References 120 publications

Detailed balance, internal consistency, and energy conservation in fragment orbital-based surface hopping

Detailed balance, internal consistency, and energy conservation in fragment orbital-based surface hopping

Subsystem density-functional theory as an effective tool for modeling ground and excited states, their dynamics and many-body interactions

Serenity: A subsystem quantum chemistry program

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