Density-Dependent Onset of the Long-Range Exchange: A Key to Donor–Acceptor Properties

Modrzejewski, Marcin; Rajchel, Łukasz; Chałasiński, Grzegorz; Szczȩśniak, M. M.

doi:10.1021/jp4088404

Cited by 32 publications

(56 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…On the other hand, absorbing the DD by the optimal tuning procedure in LRC functionals leads to almost perfect correspondence between the HL orbital gaps and the (accurate) fundamental gaps from self-consistent field (SCF) computations. 58,74,84,85 In Fig. 5, we present correlation between the dispersion energy, E (2) disp , and HL gaps for homodimers from the A24 data set.…”

Section: A24 and Di6-04 Test Resultsmentioning

confidence: 99%

“…The first one is related to the strong dependence of SAPT terms on the value of range-separation parameter which makes optimization of ω with good precision a necessity. 20 For large molecular systems, combining LRC-SAPT with more effective functional tuning schemes, such as ω GDD , 74 is recommended. The second prerequisite is related to the applicability of the optimally tuned LRC functionals themselves.…”

Section: Discussionmentioning

confidence: 99%

“…This behavior was first observed by Körzdörfer et al and attributed to the varying extent of the π -conjugated character of the system. 58 An alternative globaldensity-dependent (GDD) tuning procedure, termed ω GDD , as proposed by Modrzejewski et al 74 easily ameliorates this spurious behavior (Fig. 1).…”

Section: A Polarizabilities Of Long Chainsmentioning

confidence: 99%

See 2 more Smart Citations

Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

Hapka

Rajchel

Modrzejewski

et al. 2014

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

The aim of this study is to present a performance test of optimally tuned long-range corrected (LRC) functionals applied to the symmetry-adapted perturbation theory (SAPT). In the present variant, the second-order energy components are evaluated at the coupled level of theory. We demonstrate that the generalized Kohn-Sham (GKS) description of monomers with optimally tuned LRC functionals may be essential for the quality of SAPT interaction energy components. This is connected to the minimization of a many-electron self-interaction error and exemplified by two model systems: polyacetylenes of increasing length and stretching of He 3 (+). Next we provide a comparison of SAPT approaches based on Kohn-Sham and GKS description of the monomers. We show that LRC leads to results better or comparable with the hitherto prevailing asymptotically corrected functionals. Finally, we discuss the advantages and possible limitations of SAPT based on LRC functionals.

show abstract

Section: A24 and Di6-04 Test Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

Hapka

Rajchel

Modrzejewski

et al. 2014

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

show abstract

“…105 In fact, a clear dependence of the optimal range-separation parameter with the conjugation length of polymers was found. Although γ is practically found by application of the IP criterion (Eq.…”

mentioning

confidence: 96%

Charge-transfer excited states in phosphorescent organo-transition metal compounds: a difficult case for time dependent density functional theory?

2015

View full text Add to dashboard Cite

Figure 0: TOC Entry -Synopsis: A series of 17 platinum (II) and iridium (III) complexes have been investigated theoretically and experimentally to elucidate the charge-transfer character in emission from the lowest triplet state. Time-dependent density functional theory is found to be surprisingly accurate for metal-to-ligand transitions. ABSTRACTLight emitting organo-transition metal complexes have found widespread use in the past. The computational modelling of such compounds is often based on time-dependent density functional theory (TDDFT), which enjoys popularity due to its numerical efficiency and simple black-box character. It is well known, however, that TDDFT notoriously underestimates energies of charge-transfer excited states which are prominent in phosphorescent metal-organic compounds. In this study, we investigate whether TDDFT is providing a reliable description of the electronic properties in these systems. To this end, we compute 0-0 triplet state energies for a series of 17 pseudo-square planar platinum (II) and pseudo-octahedral iridium (III) complexes that are known to feature quite different localization * characteristics ranging from ligand-centered (LC) to metal-to-ligand charge transfer (MLCT) transitions. The calculations are performed with conventional semi-local and hybrid functionals as well as with optimally tuned range-separated functionals that were recently shown to overcome the charge transfer problem in TDDFT. We compare our results against low temperature experimental data and propose a criterion to classify excited states based on wave function localization. In addition, singlet absorption energies and singlet-triplet splittings are evaluated for a subset of the compounds and are also validated against experimental data. Our results indicate that for the investigated complexes charge-transfer is much less pronounced than previously believed.

show abstract

“…42 An optimal choice of the distance at which the long range is to commence may include setting the value of range separation parameter to satisfy the condition that a negative of the HOMO energy (ε HOMO ) equals IP 43 or evaluating the average distance between an outer electron and its exchange hole. 44 Such tuning leads to two desirable properties of a functional: HOMO and LUMO of the GKS scheme become the IP and EA, respectively, and the functional gains the piecewise linear dependence with respect to fractional electrons. As the added benefit, the exchange-correlation (xc) potential acquires the proper asymptote.…”

Section: Introductionmentioning

confidence: 99%

Density functional theory approach to gold-ligand interactions: Separating true effects from artifacts

Koppen

Hapka

Modrzejewski

et al. 2014

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

Donor-acceptor interactions are notoriously difficult and unpredictable for conventional density functional theory (DFT) methodologies. This work presents a reliable computational treatment of gold-ligand interactions of the donor-acceptor type within DFT. These interactions require a proper account of the ionization potential of the electron donor and electron affinity of the electron acceptor. This is accomplished in the Generalized Kohn Sham framework that allows one to relate these properties to the frontier orbitals in DFT via the tuning of range-separated functionals. A donor and an acceptor typically require different tuning schemes. This poses a problem when the binding energies are calculated using the supermolecular method. A two-parameter tuning for the monomer properties ensures that a common functional, optimal for both the donor and the acceptor, is found. A reliable DFT approach for these interactions also takes into account the dispersion contribution. The approach is validated using the water dimer and the (HAuPH3)2 aurophilic complex. Binding energies are computed for Au4 interacting with the following ligands: SCN(-), benzenethiol, benzenethiolate anion, pyridine, and trimethylphosphine. The results agree for the right reasons with coupled-cluster reference values.

show abstract

Density-Dependent Onset of the Long-Range Exchange: A Key to Donor–Acceptor Properties

Cited by 32 publications

References 58 publications

Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

Charge-transfer excited states in phosphorescent organo-transition metal compounds: a difficult case for time dependent density functional theory?

Density functional theory approach to gold-ligand interactions: Separating true effects from artifacts

Contact Info

Product

Resources

About