Accurate and efficient DFT-based diabatization for hole and electron transfer using absolutely localized molecular orbitals.

  title={Accurate and efficient DFT-based diabatization for hole and electron transfer using absolutely localized molecular orbitals.},
  author={Yuezhi Mao and Andr{\'e}s Montoya-Castillo and Thomas E. Markland},
  journal={The Journal of chemical physics},
  volume={151 16},
Diabatic states and the couplings between them are important for quantifying, elucidating, and predicting the rates and mechanisms of many chemical and biochemical processes. Here, we propose and investigate approaches to accurately compute diabatic couplings from density functional theory (DFT) using absolutely localized molecular orbitals (ALMOs). ALMOs provide an appealing approach to generate variationally optimized diabatic states and obtain their associated forces, which allows for the… 
8 Citations

Improved Projection-Operator Diabatization Schemes for the Calculation of Electronic Coupling Values.

This work reformulates the DFT-based projection-operator diabatization method within a simple tight-binding model to generate diabats with increased localization, yielding a proper basis set convergence and improved performance for the general Hab11 benchmark set.

Nuclear-Electronic Orbital Multistate Density Functional Theory.

The nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) method is presented as a strategy to include both static and dynamical electron-proton correlation in hydrogen tunneling dynamics.

Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation

The modulation of intermolecular interactions upon aggregation induces changes in excited state properties of organic molecules that can be detrimental for some optoelectronic applications but can be

Natural Charge-Transfer Analysis: Eliminating Spurious Charge-Transfer States in Time-Dependent Density Functional Theory via Diabatization, with Application to Projection-Based Embedding.

This work introduces an automated diabatization that enables fast and effective screening of the CTTS acceptor space in bulk solution and introduces "natural charge-transfer orbitals" that provide a means to isolate orbitals that are most likely to participate in a CTTS excitation.

Exact-two-component block-localized wave function: A simple scheme for the automatic computation of relativistic ΔSCF.

This article extends the generalized block-localized wave function technique to a relativistic two-component framework and demonstrates that time-reversal symmetry is roughly maintained when using Hartree-Fock, but less so when using Kohn-Sham density functional theory.

Analytical gradients for nuclear-electronic orbital multistate density functional theory: Geometry optimizations and reaction paths.

Hydrogen tunneling plays a critical role in many biologically and chemically important processes. The nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) method was developed

Path Integral Quantum Mechanics: from the basics to the latest developments

This work is part of a joint doctoral program in condensed matter physics and theoretical chemistry that aims at simulating the quantum dynamics of light nuclei in materials and molecular systems.



Approximate DFT-based methods for generating diabatic states and calculating electronic couplings: models of two and more states.

Four types of density functional theory (DFT)-based approaches for the approximate construction of diabatic states and the evaluation of electronic couplings between these states are assessed and it is shown that the first three approaches provide a good description for long-distance intermolecular electron transfer (ET) reactions.

Extracting electron transfer coupling elements from constrained density functional theory.

A method is presented for calculating the electronic coupling matrix element (Hab) based on constrained DFT and completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases.

Ultrafast Estimation of Electronic Couplings for Electron Transfer between π-Conjugated Organic Molecules.

It is shown that a single such relation can be established for a large number of different π-conjugated organic molecules, leading to speedups of 6 orders of magnitude with respect to reference DFT calculations, with little loss of accuracy in the regime relevant to charge transport in organics.

Direct calculation of electron transfer parameters through constrained density functional theory.

An analytic expression for the forces in constrained DFT and their implementation in geometry optimization is presented, a prerequisite for the calculation of electron transfer parameters.

Electronic Couplings for Charge Transfer across Molecule/Metal and Molecule/Semiconductor Interfaces: Performance of the Projector Operator-Based Diabatization Approach

One principal parameter determining charge transfer rates between molecules and metals is the electronic coupling strength between the discrete electronic states of the molecule and the band states

Probing non-covalent interactions with a second generation energy decomposition analysis using absolutely localized molecular orbitals.

This second generation ALMO-EDA is variational and employs valid antisymmetric electronic wavefunctions to produce all five contributions listed above, and all have non-trivial complete basis set limits.

Electronic couplings for molecular charge transfer: benchmarking CDFT, FODFT, and FODFTB against high-level ab initio calculations.

Applications to dimers outside the database suggests that the same scaling procedure significantly improves the FodFT and FODFTB results for larger π-conjugated systems relevant to organic semiconductors and DNA.

Critical analysis of fragment-orbital DFT schemes for the calculation of electronic coupling values.

A systematic investigation of the influence of exact exchange on the electronic coupling values shows that the use of hybrid functionals in FO-DFT calculations improves the electronic couplings, giving values close to or even better than more sophisticated constrained DFT calculations.

Unrestricted absolutely localized molecular orbitals for energy decomposition analysis: theory and applications to intermolecular interactions involving radicals.

This work reports a generalization of the absolutely localized molecular orbital (ALMO) energy decomposition analysis (EDA) to open shell fragments, described by self-consistent field methods, such as standard density functional theory.

Unravelling the origin of intermolecular interactions using absolutely localized molecular orbitals.

The newly proposed EDA method is used to understand the fundamental aspects of intermolecular interactions such as the degree of covalency in the hydrogen bonding in water and the contributions of forward and back-donation in synergic bonding in metal complexes.