Whereas RSH functionals such as LRC-PBE are attempts to add 100% LR Hartree-Fock exchange with minimal perturbation to the original functional (PBE, in this example), other RSH functionals are of a more empirical nature and their range-separation parameters have been carefully parameterized along with all of the other parameters in the functional. These cases are functionals are discussed first, in Section 5.6.1, because their range-separation parameters should be taken as fixed. User-defined values of the range-separation parameter are discussed in Section 5.6.2, and Section 5.6.3 discusses a procedure for which an optimal, system-specific value of this parameter ( or ) can be chosen for functionals such as LRC-PBE or LRC-PBE.

Semi-empirical RSH functionals for which the range-separation parameter should be considered fixed include the B97, B97X, and B97X-D functionals developed by Chai and Head-Gordon;[Chai and Head-Gordon(2008a), Chai and Head-Gordon(2008b)] B97X-V and B97M-V from Mardirossian and Head-Gordon;[Mardirossian and Head-Gordon(2014), Mardirossian and Head-Gordon(2016)] M11 from Peverati and Truhlar;[Peverati and Truhlar(2011b)] B97X-D3, M05-D, and M06-D3 from Chai and coworkers;[Lin et al.(2012)Lin, Tsai, Li, and Chai, Lin et al.(2013)Lin, Li, Mao, and Chai] and the screened exchange functionals N12-SX and MN12-SX from Truhlar and co-workers.[Peverati and Truhlar(2012d)] More recently, Mardirossian and Head-Gordon developed two RSH functionals, B97X-V and B97M-V, via a combinatorial approach by screening over 100,000 possible functionals in the first case and over 10 billion possible functionals in the second case. Both of the latter functionals use the VV10 non-local correlation functional in order to improve the description of non-covalent interactions and isomerization energies. B97M-V is a 12-parameter meta-GGA with 15% short-range exact exchange and 100% long-range exact exchange and is one of the most accurate functionals available through rung 4 of Jacob’s Ladder, across a wide variety of applications. This has been verified by benchmarking the functional on nearly 5000 data points against over 200 alternative functionals available in Q-Chem.[Mardirossian and Head-Gordon(2016)]

As pointed out in Ref. Dreuw:2003 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 B3LYP[Becke(1993), Stephens et al.(1994)Stephens, Devlin, Chabolowski, and Frisch] and PBE0[Adamo et al.(1999)Adamo, Scuseria, and Barone] 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.[Lange and Herbert(2007), Lange and Herbert(2009)] 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).[Lange and Herbert(2007)] 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. eq:RSHGGA) 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. (). In the limit , the LRC functional in Eq. eq:RSHGGA 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.[Lange et al.(2008)Lange, Rohrdanz, and Herbert, Rohrdanz and Herbert(2008)]

Evaluation of the short- and long-range HF exchange energies is straightforward,[Adamson et al.(1999)Adamson, Dombroski, and Gill] 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,[Iikura et al.(2001)Iikura, Tsuneda, Yanai, and Hirao, Song et al.(2007)Song, Hirosawa, Tsuneda, and Hirao] called B88 and PBE in Q-Chem,[Richard and Herbert(2011)] and an alternative formulation of short-range PBE exchange proposed by Scuseria and co-workers,[Henderson et al.(2008)Henderson, Janesko, and Scuseria] which is known as PBE. These functionals are available in Q-Chem thanks to the efforts of the Herbert group.[Rohrdanz and Herbert(2008), Rohrdanz et al.(2009)Rohrdanz, Martins, and Herbert] By way of notation, the terms “PBE”, “PBE”, *etc.*, refer only to the short-range exchange functional, in Eq. eq:RSHGGA. These functionals could be used in “screened exchange” mode, as described in Section 5.3, as for example in the HSE03 functional,[Heyd et al.(2003)Heyd, Scuseria, and Ernzerhof] 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.[Lange et al.(2008)Lange, Rohrdanz, and Herbert] However, certain results depend sensitively upon the value of the range-separation parameter ,[Lange et al.(2008)Lange, Rohrdanz, and Herbert, Rohrdanz and Herbert(2008), Rohrdanz et al.(2009)Rohrdanz, Martins, and Herbert, Lange and Herbert(2009), Uhlig et al.(2014)Uhlig, Herbert, Coons, and Jungwirth] 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.

LRC_DFT

Controls the application of long-range-corrected DFT

TYPE:

LOGICAL

DEFAULT:

FALSE

OPTIONS:

FALSE (or 0)

Do not apply long-range correction.

TRUE (or 1)

Add 100% long-range Hartree-Fock exchange to the requested functional.

RECOMMENDATION:

The

$remvariable OMEGA must also be specified, in order to set the range-separation parameter.

OMEGA

Sets the range-separation parameter, , also known as , in functionals based on Hirao’s RSH scheme.

TYPE:

INTEGER

DEFAULT:

No default

OPTIONS:

Corresponding to , in units of bohr

RECOMMENDATION:

None

COMBINE_K

Controls separate or combined builds for short-range and long-range K

TYPE:

LOGICAL

DEFAULT:

FALSE

OPTIONS:

FALSE (or 0)

Build short-range and long-range K separately (twice as expensive as a global hybrid)

TRUE (or 1)

Build short-range and long-range K together ( as expensive as a global hybrid)

RECOMMENDATION:

Most pre-defined range-separated hybrid functionals in Q-Chem use this feature by default. However, if a user-specified RSH is desired, it is necessary to manually turn this feature on.

**Example 5.47** Application of LRC-BOP to .

$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.*[Rohrdanz et al.(2009)Rohrdanz, Martins, and Herbert] 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. eq:RSHGGA) and bohr were obtained,[Rohrdanz et al.(2009)Rohrdanz, Martins, and Herbert] 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 .[Lange and Herbert(2009), Rohrdanz et al.(2009)Rohrdanz, Martins, and Herbert] In such cases (and maybe in general), the “tuning” procedure described in Section 5.6.3 is recommended.

**Example 5.48** Application of LRC-PBEh to the – dimer at 5 Å separation.

$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 discontinuity[Cohen et al.(2008)Cohen, Mori-Sánchez, and Yang, Mori-Sánchez and Cohen(2014)]) at integer values of , but in practice these plots bow away from straight-line segments.[Cohen et al.(2008)Cohen, Mori-Sánchez, and Yang] Examination of such plots has been suggested as a means to adjust the fraction of short-range exchange in an LRC functional,[Autschbach and Srebro(2014)] while the range-separation parameter is tuned as described in Section 5.6.3.

**Example 5.49** Example of a DFT job with a fractional number of electrons. Here, we make the anion of fluoride by subtracting a fraction of an electron from the HOMO of F.

$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

FRACTIONAL_ELECTRON

Add or subtract a fraction of an electron.

TYPE:

INTEGER

DEFAULT:

0

OPTIONS:

0

Use an integer number of electrons.

Add electrons to the system.

RECOMMENDATION:

Use only if trying to generate plots. If , a fraction of an electron is removed from the system.

Whereas the range-separation parameters for the functionals described in Section 5.6.1 are wholly empirical in nature and should not be adjusted, for the functionals described in Section 5.6.2 some adjustment *was* suggested, especially for TDDFT calculations and for any properties that require interpretation of orbital energies, *e.g.*, HOMO/LUMO gaps. This adjustment can be performed in a non-empirical, albeit system-specific way, by “tuning” the value of in order to satisfy certain criteria that ought rigorously to be satisfied by an exact density functional.

System-specific optimization of is based on the Koopmans condition that would be satisfied for the exact density functional, namely, that for an -electron molecule[Baer et al.(2010)Baer, Livshits, and Salzner]

(5.24) |

In other words, the HOMO eigenvalue should be equal to minus the ionization energy (IE), where the latter is defined by a SCF procedure.[van Gisbergen et al.(1996)van Gisbergen, Osinga, Gritsenko, van Leeuwen, Snijders, and Baerends, Wu et al.(2003)Wu, Ayers, and Yang] When an RSH functional is used, all of the quantities in Eq. eq:IP-tuning are -dependent, so this parameter is adjusted until the condition in Eq. eq:IP-tuning is met, which requires a sequence of SCF calculations on both the neutral and ionized species, using different values of . For proper description of charge-transfer states, Baer and co-workers[Baer et al.(2010)Baer, Livshits, and Salzner] suggest finding the value of that (to the extent possible) satisfies both Eq. eq:IP-tuning for the neutral donor molecule and its analogue for the *anion* of the acceptor species. Note that for a given approximate density functional, there is no guarantee that the IE condition can actually be satisfied for *any* value of , but in practice it usually can be, and published benchmarks suggest that this system-specific approach affords the most accurate values of IEs and TDDFT excitation energies.[Livshits and Baer(2007), Salzner and Baer(2009), Baer et al.(2010)Baer, Livshits, and Salzner] It should be noted, however, that the optimal value of can very dramatically with system size, *e.g.*, it is very different for the cluster anion (HO) than it is for cluster (HO).[Uhlig et al.(2014)Uhlig, Herbert, Coons, and Jungwirth]

A script that optimizes , called `OptOmegaIPEA.pl`, is located in the *$QC/bin* directory. The script scans over the range 0.1–0.8 bohr, corresponding to values of the *$rem* variable OMEGA in the range 100–800. See the script for the instructions how to modify the script to scan over a wider range. To execute the script, you need to create three inputs for a BNL job using the same geometry and basis set, for a neutral molecule (`N.in`), its anion (`M.in`), and its cation (`P.in`), and then run the command

OptOmegaIPEA.pl >& optomega

which both generates the input files (`N_*`, `P_*`, `M_*`) and runs Q-Chem on them, writing the optimization output into `optomega`. This script applies the IE condition to both the neutral molecule and its anion, minimizing the sum of for these two species. A similar script, `OptOmegaIP.pl`, uses Eq. eq:IP-tuning for the neutral molecule only.

**Note: ** (i) If the system does not have positive EA, then the tuning should be done according to the IP condition only. The IP/EA script will yield an incorrect value of in such cases.

(ii) In order for the scripts to work, one must specify SCF_FINAL_PRINT = 1 in the inputs. The scripts look for specific regular expressions and will not work correctly without this keyword.

Although the tuning procedure was originally developed by Baer and co-workers using the BNL functional,[Livshits and Baer(2007), Salzner and Baer(2009), Baer et al.(2010)Baer, Livshits, and Salzner] it has more recently been applied using functionals such as LRC-PBE (see, *e.g.*, Ref. Uhlig:2014), and the scripts will work with functionals other than BNL.

The value of range-separation parameter based on IP tuning procedure () exhibits a troublesome dependence on system size.[Uhlig et al.(2014)Uhlig, Herbert, Coons, and Jungwirth, Garrett et al.(2014)Garrett, Vazquez, Egri, Wilmer, Johnson, Robinson, and Isborn, Vazquez and Isborn(2015), Coons et al.(2016)Coons, You, and Herbert, Oviedo et al.(2016)Oviedo, Ilawe, and Wong] An alternative method to select is the global density-dependent (GDD) tuning procedure,[Modrzejewski et al.(2013)Modrzejewski, Rajchel, Chalasinski, and Szczesniak] in which the optimal value

(5.25) |

is related to the average of the distance between an electron in the outer regions of a molecule and the exchange hole in the region of localized valence orbitals. The quantity is an empirical parameter for a given LRC functional, which was determined for LRC-PBE () and LRC-PBEh () using the def2-TZVPP basis set.[Modrzejewski et al.(2013)Modrzejewski, Rajchel, Chalasinski, and Szczesniak] (A slightly different value, , was determined for Q-Chem’s implementation of LRC-PBE.[Lao and Herbert()]) Since LRC-PBE() provides a better description of polarizabilities in polyacetylene as compared to [Hapka et al.(2014)Hapka, Rajchel, Modrzejewski, Chałasiǹski, and Szczȩśniak], it is anticipated that using in place of may afford more accurate molecular properties, especially in conjugated systems. GDD tuning of an RSH functional is involving by setting the *$rem* variable OMEGA_GDD = TRUE. The electron density is obviously needed to compute in Eq. eq:wgdd and this is accomplished using the converged SCF density computed using the RSH functional with the value of given by the *$rem* variable OMEGA. The value of therefore depends, in principle, upon the value of OMEGA, although in practice it is not very sensitive to this value.

OMEGA_GDD

Controls the application of tuning for long-range-corrected DFT

TYPE:

LOGICAL

DEFAULT:

FALSE

OPTIONS:

FALSE (or 0)

Do not apply tuning.

TRUE (or 1)

Use tuning.

RECOMMENDATION:

The

$remvariable OMEGA must also be specified, in order to set the initial range-separation parameter.

OMEGA_GDD_SCALING

Sets the empirical constant in tuning procedure.

TYPE:

INTEGER

DEFAULT:

885

OPTIONS:

Corresponding to .

RECOMMENDATION:

The quantity = 885 was determined by Lao and Herbert in Ref. Lao:2018 using LRC-PBE and def2-TZVPP augmented with diffuse functions on non-hydrogen atoms that are taken from Dunning’s aug-cc-pVTZ basis set.

**Example 5.50** Sample input illustrating a calculation to determine the value for LRC-PBE based on the tuning procedure.

$comment The initial omega value has to set. $end $rem exchange gen basis aug-cc-pvdz lrc_dft true omega 300 omega_gdd true $end $xc_functional x wPBE 1.0 c PBE 1.0 $end $molecule 0 1 O -0.042500 0.091700 0.110000 H 0.749000 0.556800 0.438700 H -0.825800 0.574700 0.432500 $end