Assessment of asymptotically corrected model potentials for charge-transfer-like excitations in oligoacenes

Abstract

We examine the performance of the asymptotically corrected model potential scheme on the two lowest singlet excitation energies of acenes with different number of linearly fused benzene rings (up to 5), employing both the real-time time-dependent density functional theory and the frequency-domain formulation of linear-response time-dependent density functional theory. The results are compared with the experimental data and those calculated by long-range corrected hybrid functionals and others. The long-range corrected hybrid scheme is shown to outperform the asymptotically corrected model potential scheme for charge-transfer-like excitations.

The van der Waals interactions in rare-gas dimers: the role of interparticle interactions

“…In Figures 3 and 5, compared to the highly accurate CCSD(T) results, LDA and PBE perform reasonably well for sufficiently short-range interparticle interactions, whereas they perform poorly for long-range interparticle interactions. Accordingly, our findings are also in support of the key feature of the LC hybrid functionals for systems with Coulomb interactions, which have recently been found to provide supreme performance for a very wide range of applications [57,58], especially for problems related to the asymptote of the XC potential [59][60][61][62][63][64][65][66], self-interaction errors [67,68], fundamental gaps [69][70][71][72][73][74][75][76][77][78][79][80][81][82], and charge-transfer excitations [83][84][85][86][87][88][89]. Besides, empirical atom-atom dispersion potentials [51,55,56,[90][91][92] or MP2 correlation energy [43,53,[93][94]…”

Electrostatic Field-Induced Oscillator Strength Focusing in Molecules

“…The B3LYP hybrid exchange-correlation functional suffers from spurious electron self-interaction errors, as do other global hybrid functionals, with consequent errors in the description of charge-transfer (CT) states. , The errors inherent in the exchange-correlation functional propagate in the TDDFT method, affecting both the energies and the long-distance behavior of the CT excited states. , The CS00 asymptotic correction to B3LYP , was shown to improve the description of CT excited states in several cases, , and further improvement may arise from its combination with the TDA . However, in general, CS00 and other asymptotic corrections are not expected to correct both of the deficiencies in the TDDFT description of CT excited states. , Range-separated hybrid functionals can produce CT excited states of significantly higher quality compared to global hybrid functionals, although they suffer from the use of a fixed range-separation parameter and increase the computational cost, especially when the density functional requires the use of large basis sets . Furthermore, poor performance of oscillator strength calculations with some range-separated functionals was reported, e.g., for C 2 H 4 .…”

Short- and long-range corrected hybrid density functionals with the D3 dispersion corrections

“…Even if the asymptote problems can be properly resolved by the recently developed semilocal density functionals with correct asymptotic behavior [42][43][44][45][46] and asymptotically corrected model XC potentials [47][48][49][50][51], the SIE problems may remain unresolved [52]. Besides, semilocal density functionals are inaccurate for charge-transfer (CT) excitation energies [41,42,[52][53][54][55][56][57][58][59][60][61], due to the lack of a space-and frequency-dependent discontinuity in the adiabatic XC kernel adopted in TDDFT [62].…”