Impact of non‐empirically tuning the range‐separation parameter of long‐range corrected hybrid functionals on ionization potentials, electron affinities, and fundamental gaps

Non‐empirically tuning the range‐separation parameter (ω) of long‐range corrected (LC) hybrid functionals in improving the accuracy of vertical ionization potentials (IPs), vertical electron affinities (EAs), and fundamental gaps (FGs) is investigated. Use of default ω values gives the best overall property predictions employing the Δ self‐consistent field (ΔSCF) approach, if sufficiently large basis set is used. Upon tuning, IP (HOMO) (i.e., the IP estimated from the negative of HOMO energy via DFT Koopmans’ theorem) with the IP (ΔSCF) (i.e., the IP obtained from the ΔSCF approach) the accuracy of IP (HOMO) significantly improves however a reciprocal phenomenon is not observed. An interesting observation is that EA (LUMO) (i.e., the EA estimated from the negative of LUMO energy) is more accurate than EA (ΔSCF), if the ω value is in the range of 0.30 to 0.50 bohr−1. © 2018 Wiley Periodicals, Inc.

[1]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[2]  R. Bartlett,et al.  A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples , 1982 .

[3]  Leeor Kronik,et al.  Fundamental and excitation gaps in molecules of relevance for organic photovoltaics from an optimally tuned range-separated hybrid functional , 2011 .

[4]  Assessment of density functional methods for exciton binding energies and related optoelectronic properties , 2015, 1508.07396.

[5]  M Belén Oviedo,et al.  Accurate Electron Affinities and Orbital Energies of Anions from a Nonempirically Tuned Range-Separated Density Functional Theory Approach. , 2017, Journal of chemical theory and computation.

[6]  A. Zunger,et al.  Self-interaction correction to density-functional approximations for many-electron systems , 1981 .

[7]  M. Head‐Gordon,et al.  Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. , 2008, Physical chemistry chemical physics : PCCP.

[8]  M. Head‐Gordon,et al.  Systematic optimization of long-range corrected hybrid density functionals. , 2008, The Journal of chemical physics.

[9]  Kerstin Andersson,et al.  Second-order perturbation theory with a CASSCF reference function , 1990 .

[10]  Kimihiko Hirao,et al.  On Koopmans' theorem in density functional theory. , 2010, The Journal of chemical physics.

[11]  Jean-Luc Brédas,et al.  Long-range corrected hybrid functionals for π-conjugated systems: dependence of the range-separation parameter on conjugation length. , 2011, The Journal of chemical physics.

[12]  D. Gaspar,et al.  OLED fundamentals : materials, devices, and processing of organic light-emitting diodes , 2015 .

[13]  Andreas Savin,et al.  Density functionals for the Yukawa electron-electron interaction , 1995 .

[14]  Jean-Luc Brédas,et al.  Organic electronic materials: recent advances in the DFT description of the ground and excited states using tuned range-separated hybrid functionals. , 2014, Accounts of chemical research.

[15]  V. Barone,et al.  Toward reliable density functional methods without adjustable parameters: The PBE0 model , 1999 .

[16]  Jeng-Da Chai,et al.  Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections. , 2012, Journal of chemical theory and computation.

[17]  Patrick Rinke,et al.  Accurate Ionization Potentials and Electron Affinities of Acceptor Molecules II: Non-Empirically Tuned Long-Range Corrected Hybrid Functionals. , 2016, Journal of chemical theory and computation.

[18]  Bryan M. Wong,et al.  Optoelectronic and Excitonic Properties of Oligoacenes: Substantial Improvements from Range-Separated Time-Dependent Density Functional Theory , 2010, Journal of chemical theory and computation.

[19]  J. Perdew,et al.  Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy , 1982 .

[20]  K. Hirao,et al.  A long-range correction scheme for generalized-gradient-approximation exchange functionals , 2001 .

[21]  Computational study on thermally activated delayed fluorescence of donor–linker–acceptor network molecules , 2016 .

[22]  Jeng-Da Chai,et al.  Assessment of density functional methods with correct asymptotic behavior. , 2012, Physical chemistry chemical physics : PCCP.

[23]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[24]  M. Head‐Gordon,et al.  Reprint of: A fifth-order perturbation comparison of electron correlation theories , 2013 .

[25]  R. Baer,et al.  A well-tempered density functional theory of electrons in molecules. , 2007, Physical chemistry chemical physics : PCCP.

[26]  K. Hirao,et al.  A long-range-corrected time-dependent density functional theory. , 2004, The Journal of chemical physics.

[27]  Takao Tsuneda,et al.  On low‐lying excited states of extended nanographenes , 2017, J. Comput. Chem..

[28]  K. Burke,et al.  Rationale for mixing exact exchange with density functional approximations , 1996 .

[29]  Shiang-Tai Lin,et al.  Assessing the role of Hartree‐Fock exchange, correlation energy and long range corrections in evaluating ionization potential, and electron affinity in density functional theory , 2017, J. Comput. Chem..

[30]  Leeor Kronik,et al.  Excitation Gaps of Finite-Sized Systems from Optimally Tuned Range-Separated Hybrid Functionals. , 2012, Journal of chemical theory and computation.

[31]  Bryan M. Wong,et al.  Nonempirically Tuned Range-Separated DFT Accurately Predicts Both Fundamental and Excitation Gaps in DNA and RNA Nucleobases , 2012, Journal of chemical theory and computation.

[32]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[33]  J. Janak,et al.  Proof that ? E /? n i =e in density-functional theory , 1978 .

[34]  M. Head‐Gordon,et al.  Optimal operators for Hartree-Fock exchange from long-range corrected hybrid density functionals , 2008 .

[35]  Kerwin Hui,et al.  Short- and long-range corrected hybrid density functionals with the D3 dispersion corrections. , 2016, The Journal of chemical physics.

[36]  John P. Perdew,et al.  Exact differential equation for the density and ionization energy of a many-particle system , 1984 .