As pointed out in Ref. 234 and elsewhere, the description of charge-transfer excited states within density functional theory (or more precisely, time-dependent DFT, which is discussed in Section 7.3) requires full (100%) non-local HF exchange, at least in the limit of large donor–acceptor distance. Hybrid functionals such as B3LYP54, 918 and PBE05 that are well-established and in widespread use, however, employ only 20% and 25% HF exchange, respectively. While these functionals provide excellent results for many ground-state properties, they cannot correctly describe the distance dependence of charge-transfer excitation energies, which are enormously underestimated by most common density functionals. This is a serious problem in any case, but it is a catastrophic problem in large molecules and in non-covalent clusters, where TDDFT often predicts a near-continuum of spurious, low-lying charge transfer states.528, 530 The problems with TDDFT’s description of charge transfer are not limited to large donor–acceptor distances, but have been observed at 2 Å separation, in systems as small as uracil–(HO).528 Rydberg excitation energies also tend to be substantially underestimated by standard TDDFT.
One possible avenue by which to correct such problems is to parameterize functionals that contain 100% HF exchange, though few such functionals exist to date. An alternative option is to attempt to preserve the form of common GGAs and hybrid functionals at short range (i.e., keep the 25% HF exchange in PBE0) while incorporating 100% HF exchange at long range, which provides a rigorously correct description of the long-range distance dependence of charge-transfer excitation energies, but aims to avoid contaminating short-range exchange-correlation effects with additional HF exchange. The separation is accomplished using the range-separation ansatz that was introduced in Section 5.3. In particular, functionals that use 100% HF exchange at long range ( in Eq. (5.13)) are known as “long-range-corrected” (LRC) functionals. An LRC version of PBE0 would, for example, have .
To fully specify an LRC functional, one must choose a value for the range separation parameter in Eq. (5.12). In the limit , the LRC functional in Eq. (5.13) reduces to a non-RSH functional where there is no “SR” or “LR”, because all exchange and correlation energies are evaluated using the full Coulomb operator, . Meanwhile the limit corresponds to a new functional, . Full HF exchange is inappropriate for use with most contemporary GGA correlation functionals, so the latter limit is expected to perform quite poorly. Values of bohr are likely not worth considering, according to benchmark tests.534, 825
Evaluation of the short- and long-range HF exchange energies is straightforward,9 so the crux of any RSH functional is the form of the short-range GGA exchange functional, and several such functionals are available in Q-Chem. These include short-range variants of the B88 and PBE exchange described by Hirao and co-workers,413, 900 called B88 and PBE in Q-Chem,819 and an alternative formulation of short-range PBE exchange proposed by Scuseria and co-workers,370 which is known as PBE. These functionals are available in Q-Chem thanks to the efforts of the Herbert group.825, 826 By way of notation, the terms “PBE”, “PBE”, etc., refer only to the short-range exchange functional, in Eq. (5.13). These functionals could be used in “screened exchange” mode, as described in Section 5.3, as for example in the HSE03 functional,380 therefore the designation “LRC-PBE”, for example, should only be used when the short-range exchange functional PBE is combined with 100% Hartree-Fock exchange in the long range.
In general, LRC-DFT functionals have been shown to remove the near-continuum of spurious charge-transfer excited states that appear in large-scale TDDFT calculations.534 However, certain results depend sensitively upon the value of the range-separation parameter ,534, 825, 826, 530, 978 especially in TDDFT calculations (Section 7.3) and therefore the results of LRC-DFT calculations must therefore be interpreted with caution, and probably for a range of values. This can be accomplished by requesting a functional that contains some short-range GGA exchange functional (PBE or PBE, in the examples mentioned above), in combination with setting the $rem variable LRC_DFT = TRUE, which requests the addition of 100% Hartree-Fock exchange in the long-range. Basic job-control variables and an example can be found below. The value of the range-separation parameter is then controlled by the variable OMEGA, as shown in the examples below.
$comment The value of omega is 0.47 by default but can be overwritten by specifying OMEGA. $end $molecule -1 2 O 1.347338 -0.017773 -0.071860 H 1.824285 0.813088 0.117645 H 1.805176 -0.695567 0.461913 O -1.523051 -0.002159 -0.090765 H -0.544777 -0.024370 -0.165445 H -1.682218 0.174228 0.849364 $end $rem EXCHANGE LRC-BOP BASIS 6-31(1+,3+)G* LRC_DFT TRUE OMEGA 300 ! = 0.300 bohr**(-1) $end
Rohrdanz et al.826 published a thorough benchmark study of both ground- and excited-state properties using the LRC-PBEh functional, in which the “h” indicates a short-range hybrid (i.e., the presence of some short-range HF exchange). Empirically-optimized parameters of (see Eq. (5.13)) and bohr were obtained,826 and these parameters are taken as the defaults for LRC-PBEh. Caution is warranted, however, especially in TDDFT calculations for large systems, as excitation energies for states that exhibit charge-transfer character can be rather sensitive to the precise value of .530, 826 In such cases (and maybe in general), the “tuning” procedure described in Section 5.6.3 is recommended.
$comment This example uses the "optimal" parameter set discussed above. It can also be run by setting METHOD = LRC-wPBEh. $end $molecule 0 1 C 0.670604 0.000000 0.000000 C -0.670604 0.000000 0.000000 H 1.249222 0.929447 0.000000 H 1.249222 -0.929447 0.000000 H -1.249222 0.929447 0.000000 H -1.249222 -0.929447 0.000000 C 0.669726 0.000000 5.000000 C -0.669726 0.000000 5.000000 F 1.401152 1.122634 5.000000 F 1.401152 -1.122634 5.000000 F -1.401152 -1.122634 5.000000 F -1.401152 1.122634 5.000000 $end $rem EXCHANGE GEN BASIS 6-31+G* LRC_DFT TRUE OMEGA 200 ! = 0.2 a.u. CIS_N_ROOTS 4 CIS_TRIPLETS FALSE $end $xc_functional C PBE 1.00 X wPBE 0.80 X HF 0.20 $end
Both LRC functionals and also the asymptotic corrections that will be discussed in Section 5.10.1 are thought to reduce self-interaction error in approximate DFT. A convenient way to quantify—or at least depict—this error is by plotting the DFT energy as a function of the (fractional) number of electrons, , because should in principle consist of a sequence of line segments with abrupt changes in slope (the so-called derivative discontinuity175, 667) at integer values of , but in practice these plots bow away from straight-line segments.175 Examination of such plots has been suggested as a means to adjust the fraction of short-range exchange in an LRC functional,26 while the range-separation parameter is tuned as described in Section 5.6.3.
$comment Subtracting a whole electron recovers the energy of F-. Adding electrons to the LUMO is possible as well. $end $rem EXCHANGE b3lyp BASIS 6-31+G* FRACTIONAL_ELECTRON -500 ! divide by 1000 to get the fraction, -0.5 here. GEN_SCFMAN FALSE ! not yet available in new scf code $end $molecule -2 2 F $end