Show simple item record

dc.contributor.authorKörzdörfer, Thomas
dc.contributor.authorBredas, Jean-Luc
dc.date.accessioned2015-08-03T12:17:19Z
dc.date.available2015-08-03T12:17:19Z
dc.date.issued2014-04-30
dc.identifier.citationKörzdörfer, T., & Brédas, J.-L. (2014). Organic Electronic Materials: Recent Advances in the DFT Description of the Ground and Excited States Using Tuned Range-Separated Hybrid Functionals. Accounts of Chemical Research, 47(11), 3284–3291. doi:10.1021/ar500021t
dc.identifier.issn00014842
dc.identifier.doi10.1021/ar500021t
dc.identifier.urihttp://hdl.handle.net/10754/563860
dc.description.abstractDensity functional theory (DFT) and its time-dependent extension (TD-DFT) are powerful tools enabling the theoretical prediction of the ground- and excited-state properties of organic electronic materials with reasonable accuracy at affordable computational costs. Due to their excellent accuracy-to-numerical-costs ratio, semilocal and global hybrid functionals such as B3LYP have become the workhorse for geometry optimizations and the prediction of vibrational spectra in modern theoretical organic chemistry. Despite the overwhelming success of these out-of-the-box functionals for such applications, the computational treatment of electronic and structural properties that are of particular interest in organic electronic materials sometimes reveals severe and qualitative failures of such functionals. Important examples include the overestimation of conjugation, torsional barriers, and electronic coupling as well as the underestimation of bond-length alternations or excited-state energies in low-band-gap polymers.In this Account, we highlight how these failures can be traced back to the delocalization error inherent to semilocal and global hybrid functionals, which leads to the spurious delocalization of electron densities and an overestimation of conjugation. The delocalization error for systems and functionals of interest can be quantified by allowing for fractional occupation of the highest occupied molecular orbital. It can be minimized by using long-range corrected hybrid functionals and a nonempirical tuning procedure for the range-separation parameter.We then review the benefits and drawbacks of using tuned long-range corrected hybrid functionals for the description of the ground and excited states of π-conjugated systems. In particular, we show that this approach provides for robust and efficient means of characterizing the electronic couplings in organic mixed-valence systems, for the calculation of accurate torsional barriers at the polymer limit, and for the reliable prediction of the optical absorption spectrum of low-band-gap polymers. We also explain why the use of standard, out-of-the-box range-separation parameters is not recommended for the DFT and/or TD-DFT description of the ground and excited states of extended, pi-conjugated systems. Finally, we highlight a severe drawback of tuned range-separated hybrid functionals by discussing the example of the calculation of bond-length alternation in polyacetylene, which leads us to point out the challenges for future developments in this field.
dc.publisherAmerican Chemical Society (ACS)
dc.titleOrganic electronic materials: Recent advances in the dft description of the ground and excited states using tuned range-separated hybrid functionals
dc.typeArticle
dc.contributor.departmentKAUST Solar Center (KSC)
dc.contributor.departmentLaboratory for Computational and Theoretical Chemistry of Advanced Materials
dc.contributor.departmentMaterial Science and Engineering Program
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalAccounts of Chemical Research
dc.contributor.institutionComputational Chemistry, Institute of Chemistry, University of PotsdamPotsdam, Germany
dc.contributor.institutionSchool of Chemistry and Biochemistry, Center for Organic Photonics and Electronics, Georgia Institute of TechnologyAtlanta, GA, United States
kaust.personBredas, Jean-Luc
dc.date.published-online2014-04-30
dc.date.published-print2014-11-18


This item appears in the following Collection(s)

Show simple item record