A Benchmark Study of Electronic Couplings in Donor–Bridge–Acceptor Systems with the FMR-B Method

Biancardi, Alessandro; Caricato, Marco

doi:10.1021/acs.jctc.8b00029

Cited by 7 publications

(4 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In brief, an orbital localized on a specific fragment is, within the FMR-B method, called a fragment orbital. The fragment orbitals are obtained through a block diagonalization of the total Fock matrix and subsequent Löwdin transformation to ensure orthogonality. − A detailed derivation of the electronic coupling elements in terms of the FMR-B method is provided in the Supporting Information.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

Redfield Propagation of Photoinduced Electron Transfer Reactions in Vacuum and Solution

Pedersen

Rasmussen

Mikkelsen

2022

J. Chem. Theory Comput.

View full text Add to dashboard Cite

Dynamical simulations of ultrafast electron transfer reactions are of utmost interest. To allow for energy dissipation directly into an external surrounding environment, a solvent coupling model has been deduced, implemented, and utilized to describe the photoinduced electron transfer dynamics within a model triad system herein. The model is based on Redfield theory, and the environment is represented by harmonic oscillators filled with bosonic quanta. To imitate real solvents, the oscillators have been equipped with frequencies and polarization lifetimes characteristic of the corresponding solvent. The population was found to transfer through the energetically lowest electron transfer route regardless of the medium. The condensed population transfer dynamics were observed to be highly dependent on the solvent parameters. In particular, an increase in the solvent coupling entailed a detainment in the population transfer from the initially prepared diabatic state and a promotion in the population transfer through the other electron transfer route. Two explanations based on the diagonal and off-diagonal matrix elements of the Kohn−Sham Fock matrix, respectively, have been provided. The lifetime of the populated partially charge-separated state was prolonged with increasing solvent polarity, and it was explained in terms of attractive interactions between the solvent's dipole moments and the fragments' charges. The high-frequency vibrational fine-structure in the correlation function was demonstrated to be important for the transfer dynamics, and the importance of dephasing effects in polar solvents was verified and precised to concern the optical polarization of the solvents.

show abstract

Section: Theoretical Backgroundmentioning

confidence: 99%

Redfield Propagation of Photoinduced Electron Transfer Reactions in Vacuum and Solution

Pedersen

Rasmussen

Mikkelsen

2022

J. Chem. Theory Comput.

View full text Add to dashboard Cite

show abstract

“…The prevalence of rangeseparated functionals in the best set agrees with previous results. 44 M06-HF is the only global hybrid functional in this set, built using a recipe of the type 45…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…Although the unknown form of the exact functional partly makes DFT a "black box" with empirical or semiempirical components, this study identifies the combinations of factors that determine the reliability of functionals for the calculation of electronic couplings in molecular systems of diverse size and donor−acceptor distances. This study disentangles a preexisting inconvenient scenario characterized by discordant conclusions on functionals with a large amount of HF exchange 18,44 and the alarming perception that the application of DFT to a given system could just provide a continuum of coupling values depending on the amount of HF exchange used, with the real coupling value remaining thus elusive. This study identifies the small set of fundamental rules that, once taken together, allow one to build functionals with robust performance for coupling computation.…”

Section: ■ Conclusionmentioning

confidence: 99%

How To Extract Quantitative Information on Electronic Transitions from the Density Functional Theory “Black Box”

Migliore

2019

J. Chem. Theory Comput.

View full text Add to dashboard Cite

Electronic couplings and vertical excitation energies are crucial determinants of charge and excitation energy transfer rates in a broad variety of processes ranging from biological charge transfer to charge transport through inorganic materials, from molecular sensing to intracellular signaling. Density Functional Theory (DFT) is generally used to calculate these critical parameters, but the quality of the results is unpredictable because of the semiempirical nature of the available DFT approaches. This study identifies a small set of fundamental rules that enables accurate DFT computation of electronic couplings and vertical excitation energies in molecular complexes and materials. These rules are applied to predict efficient DFT approaches to coupling calculations. The result is an easy-to-use guide for reliable DFT descriptions of electronic transitions.

show abstract

“…The very first protocol for the transformation of an adiabatic basis to a diabatic basis was presented by Mikkelsen et al In this work, however, the transformation is carried out by utilizing the Fock matrix reconstruction - bridge (FMR-B) method, in which the Fock matrix in atomic orbitals is block diagonalized and subsequently Löwdin transformed in order to construct appropriate orthogonal fragment orbitals representative of the composite system. The electronic coupling elements are then calculated as the off-diagonal matrix elements of the diabatized Fock matrix. − …”

Section: Redfield Time Propagationmentioning

confidence: 99%

Solvent-Induced Symmetry Breaking of the Photoinduced Charge Transfer Dynamics in the Bridged Perylene Dimer

Ekstrøm,

Pedersen,

Mikkelsen

2023

J. Phys. Chem. A

View full text Add to dashboard Cite

The charge transfer dynamics of the bridged perylene dimer were investigated with the recently developed solvent coupling Redfield time propagation model. The results are compared with previous experimental findings to showcase the significance and applicability of the model. The charge transfer dynamics in vacuum showed that no breaking of the charge transfer direction symmetry occurred upon optical excitation, in perfect agreement with the experiment. Meanwhile, attractive solute−solvent interactions facilitated by the dipole moments of the polar solvents were observed to break the charge transfer direction symmetry. The conformational isomerism effect on the transfer dynamics manifested itself by promoting different transport channels upon solvation. Consequently, the solvent coupling Redfield time propagation model was indeed found to be able to quantitatively describe the charge transfer dynamics including exotic phenomena such as symmetry breaking of charge transfer direction.

show abstract

A Benchmark Study of Electronic Couplings in Donor–Bridge–Acceptor Systems with the FMR-B Method

Cited by 7 publications

References 65 publications

Redfield Propagation of Photoinduced Electron Transfer Reactions in Vacuum and Solution

Redfield Propagation of Photoinduced Electron Transfer Reactions in Vacuum and Solution

How To Extract Quantitative Information on Electronic Transitions from the Density Functional Theory “Black Box”

Solvent-Induced Symmetry Breaking of the Photoinduced Charge Transfer Dynamics in the Bridged Perylene Dimer

Contact Info

Product

Resources

About