English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

Diabatic states and the couplings between them are important for quantifying,elucidating, and predicting the rates and mechanisms of many chemical andbiochemical processes. Here, we propose and investigate approaches toaccurately compute diabatic couplings from density functional theory (DFT)using absolutely localized molecular orbitals (ALMOs). ALMOs provide anappealing approach to generate variationally optimized diabatic states andobtain their associated forces that allows for the relaxation of the donor andacceptor orbitals in a way that is internally consistent in how the methodtreats both the donor and acceptor states. Here, we show that one can obtainmore accurate electronic couplings between ALMO-based diabats by employing thesymmetrized transition density matrix to evaluate the exchange-correlationcontribution. We demonstrate that this approach yields accurate results incomparison to other commonly used DFT-based diabatization methods across a widearray of electron and hole transfer processes occurring in systems ranging fromconjugated organic molecules, such as thiophene and pentacene, to DNA basepairs. We also show that this approach yields accurate diabatic couplings evenwhen combined with lower tiers of the DFT hierarchy, opening the door tocombining it with quantum dynamics approaches to provide an ab initio treatmentof nonadiabatic processes in the condensed phase.

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