Density-functional theory (hyper)polarizabilities of push-pull π-conjugated systems: Treatment of exact exchange and role of correlation

Bulat, Felipe A.; Toro–Labbé, Alejandro; Champagne, Benoı̂t; Kirtman, Bernard; Yang, Weitao

doi:10.1063/1.1926275

Cited by 123 publications

(91 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These two methods include different fractions of HF exchange in different solvents, again emphasizing that the exchange energy-be it short or long range-is of critical importance to describe hyperpolarizabilities, 21,22,35 and their dependence on the media. 55,89 Additionally, the largest dependencies on the error are seen for the solvent/gas averages of differences in Table 5.…”

Section: Solvent and Frequency Effectsmentioning

confidence: 99%

“…[8][9][10][11] This has generated much interest around this kind of compounds owing to the applications of materials with large hyperpolarizabilities in nonlinear optics [12][13][14][15][16][17][18][19] (NLO), and a considerable amount of effort in this area of research has been devoted to the theoretical prediction of NLO properties via computational methods of quantum chemistry. [19][20][21][22][23][24][25][26][27][28] It was recognized early on that the theoretical determination of hyperpolarizabilities was very challenging for ab initio and semi-empirical methods. 8,12,20 The advent of modern density functional theory (DFT) methods, very successful in many areas across chemistry and materials science, does not solve this problem.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Can Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?

et al. 2014

View full text Add to dashboard Cite

The hyperpolarizabilities of five prototypical and four recently synthesized longrange charge-transfer (CT) organic compounds are calculated using short-and middlerange (SR and MR) hybrid functionals. These results are compared with data from MP2 and other DFT methods including GGAs, global hybrids, long-range corrected functionals (LC-DFT), and optimally-tuned LC-DFT. Although it is commonly believed that the overestimation of hyperpolarizabilities associated with CT excitations * To whom correspondence should be addressed

show abstract

Section: Solvent and Frequency Effectsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Can Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?

et al. 2014

View full text Add to dashboard Cite

show abstract

“…It has also been argued that correlation effects play a non-negligible role in the proper description of response properties [10]. However, evaluating the Fock integrals in exact exchange approaches increases numerical costs substantially, and the computational complexity of approaches using exact exchange with "compatible" correlation is significant [11].…”

mentioning

confidence: 99%

Electrical Response of Molecular Systems: The Power of Self-Interaction Corrected Kohn-Sham Theory

2008

View full text Add to dashboard Cite

The accurate prediction of electronic response properties of extended molecular systems has been a challenge for conventional, explicit density functionals. We demonstrate that a self-interaction correction implemented rigorously within Kohn-Sham theory via the Optimized Effective Potential (OEP) yields polarizabilities close to the ones from highly accurate wavefunction-based calculations and exceeding the quality of exact-exchange-OEP. The orbital structure obtained with the OEP-SIC functional and approximations to it are discussed.PACS numbers: 31.15. Ew,71.15.Mb,72.80.Le Gaining microscopic insight into the quantummechanical electronic effects that govern energy-and charge transfer in processes like light-harvesting, chargeseparation in organic solar cells, or the response of molecular opto-electronic devices would be extremely beneficial to the understanding of these phenomena. But the computational complexity of solving the manyelectron Schrödinger equation leaves little hope that wave-function based approaches can address these problems any time soon. The formulation of quantum mechanics without wavefunction, i.e., density functional theory (DFT) in the Kohn-Sham framework, is computationally much more efficient and allows to handle systems with up to several hundreds of electrons. Therefore, it appears as the ideal tool for investigating the above mentioned problems. However, the predictive power of DFT calculations depends crucially on the approximations made in the description of the exchange-correlation effects. Structural, ground-state molecular properties are obtained with reasonable to excellent accuracy using standard, explicit density functionals like the Local Spin Density Approximation (LSDA) or Generalized Gradient Approximations (GGAs). But these functionals notoriously fail in the description of charge transfer processes [1, 2] and associated problems like predicting the response [3] or transport [4] properties of extended molecular systems. There is, thus, a serious need for exchange-correlation approximations that allow to calculate response properties like polarizabilities of extended systems reliably on a quantitative scale and with bearable computational costs.It has been demonstrated that improvements in the density-functional description of the response of conjugated polymers can be achieved based on current density functional theory [5] and related ideas [6], or by incorporating full [3,7,8] or partial [9] exact exchange. It has also been argued that correlation effects play a non-negligible role in the proper description of response properties [10]. However, evaluating the Fock integrals in exact exchange approaches increases numerical costs substantially, and the computational complexity of approaches using exact exchange with "compatible" correlation is significant [11].In this manuscript we demonstrate that these problems can be overcome with a self-interaction correction (SIC) employed rigorously within Kohn-Sham theory. In the SIC-scheme, only direct, i.e., self-exchange int...

show abstract

“…This spectacular difference is perhaps even underestimated because the dimerization that one would find in a DFT optimization is expected to be less than the MP2 dimerization. The use of exact exchange via an optimized effective potential in a DFT method does correct this problem [47], but this work is an assessment of ADFT, not DFT.…”

Section: Dipole Moment Of Nh 2 (Ch) 24 Nomentioning

confidence: 99%

Dipole Moments From Atomic-Number-Dependent Potentials in Analytic Density-Functional Theory

Dunlap¹,

Karna²,

Zope³

2010

View full text Add to dashboard Cite

show abstract

Density-functional theory (hyper)polarizabilities of push-pull π-conjugated systems: Treatment of exact exchange and role of correlation

Cited by 123 publications

References 28 publications

Can Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?

Can Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?

Electrical Response of Molecular Systems: The Power of Self-Interaction Corrected Kohn-Sham Theory

Dipole Moments From Atomic-Number-Dependent Potentials in Analytic Density-Functional Theory

Contact Info

Product

Resources

About