6.

3 Basis 1
Sets

6.3 Basis Sets

6.3.1 Standard basis set library

There are standard basis sets that can be specified via the “simple input” feature in the keyword line.
However, any basis set that is not already included in the ORCA library can be provided either
directly in the input or through an external file. See the BASIS input block for a full list of internal
basis sets and various advanced aspects (section 9.5). Effective core potentials and their use are
described in section 6.3.3.

Table 6.3: Basis sets available on ORCA.

Pople-style basis sets
STO-3G Minimal basis set(H–I)
3-21G Pople 3-21G (H–Cs)
3-21GSP Buenker 3-21GSP (H–Ar)
4-22GSP Buenker 4-22GSP (H–Ar)
6-31G Pople 6-31G and its modifications (H–Zn)
m6-31G Modified 6-31G for 3d transition metals (Sc–Cu)
6-311G Pople 6-311G and its modifications (H–Br)
Polarization functions for the 6-31G basis set:
* or (d) One set of first polarization functions on all atoms except H
** or (d,p) One set of first polarization functions on all
atoms Further combinations: (2d), (2df), (2d,p), (2d,2p), (2df,2p), (2df,2pd)
Polarization functions for the 6-311G basis set:
All of the above plus (3df) and (3df,3pd)

Diffuse functions for the 6-31G and 6-311G basis sets:

+ before “G” Include diffuse functions on all atoms except H (e.g. 6-
31+G)
++ before “G” Include diffuse functions on all atoms. Works only when
H
polarization is already included, e.g. 6-31++G(d,p)
The def2 basis sets of the Karlsruhe group
These basis sets are all-electron for elements H–Kr, and automatically load Stuttgart-Dresden
effective core potentials for elements Rb–Rn.
def2-SVP Valence double-zeta basis set with “new” polarization
functions.
def2-SV(P) The above with slightly reduced polarization.
def2-TZVP Valence triple-zeta basis set with “new” polarization
functions. Note that this is quite similar to the older
(“def”) TZVPP for the main group elements and TZVP for
hydrogen.
def2-TZVP(-f) TZVP with f polarization removed from main group
elements. def2-TZVPP TZVPP basis set with “new” polarization functions.
def2-QZVP Polarized quadruple-zeta basis.
def2-QZVPP Accurate doubly polarized quadruple-zeta basis.
Older (“def”) Ahlrichs basis sets
All-electron basis sets for elements H–Kr.
SV Valence double-zeta basis set.
2 6 General Structure of the Input
File

SV(P) Valence double-zeta with polarization only on heavy

elements.
SVP Polarized valence double-zeta basis set.
TZV Valence triple-zeta basis set.
TZV(P) Valence triple-zeta with polarization on heavy elements.
TZVP Polarized valence triple-zeta basis set.
TZVPP Doubly polarized triple-zeta basis set.
QZVP Polarized valence quadruple-zeta basis set.
QZVPP Doubly polarized quadruple-zeta basis set.

Note: Past versions of ORCA used to load all-electron basis sets also for elements Rb–I
with the above keywords for double- and triple-zeta basis sets. The Rb–I basis sets
originated from non-relativistic all-electron basis sets of the Turbomole library (such as
“TZVPAlls”). This automatic substitution is now deprecated. However, we offer
temporarily the ability to reproduce that behavior by adding the prefix “old-” to the
above keywords, e.g. “old-TZVP”.
Diffuse def2 basis sets
Minimally augmented def2 ba- Augmented def2 basis sets by diffuse s and p functions
according
sis sets to Truhlar [1]. Recommended for general use.

ma-def2-SVP Minimally augmented def2-SVP basis set.

ma-def2-SV(P) Minimally augmented def2-SV(P) basis set.
ma-def2-TZVP Minimally augmented def2-TZVP basis set.
ma-def2-TZVP(-f) Minimally augmented def2-TZVP(-f) basis
set. ma-def2-TZVPP Minimally augmented def2-TZVPP basis set.
ma-def2-QZVPP Minimally augmented def2-QZVPP basis set.

Rappoport property-optimized Augmented def2 basis sets by diffuse functions according to

diffuse def2 basis sets Rappoport et al. [2]

def2-SVPD Diffuse def2-SVP basis set for property calculations

def2-TZVPD Diffuse def2-TZVP basis set for property calculations
def2-TZVPPD Diffuse def2-TZVPP basis set for property calculations
def2-QZVPD Diffuse def2-QZVP basis set for property calculations
def2-QZVPPD Diffuse def2-QZVPP basis set for property calculations
Karlsruhe basis sets with Dirac–Fock ECPs
These basis sets are derived from the def2-XVP ones with small modifications for 5s, 6s,
4d, and 5d elements and iodine. [3] They are optimized for the revised Dirac–Fock
ECPs (dhf-ECP) as opposed to the Wood–Boring ones (def2-ECP). Versions for two-
component methods are also available, e.g. “dhf-TZVP-2c”, however, such methods
are currently not implemented in ORCA.
dhf-SV(P) based on def2-SV(P)
dhf-SVP based on def2-SVP
dhf-TZVP based on def2-TZVP
dhf-TZVPP based on def2-TZVPP
dhf-QZVP based on def2-QZVP
dhf-QZVPP based on def2-QZVPP
6.3 Basis 3
Sets

Relativistically recontracted Karlsruhe basis sets

For use in DKH or ZORA calculations we provide adapted versions of the def2 basis sets
for the elements H–Kr (i.e., for the all-electron def2 basis sets). These basis sets
retain the original def2 exponents but have only one contracted function per angular
momentum (and hence are somewhat larger), with contraction coefficients suitable for
the respective scalar relativistic Hamiltonian. These basis sets can be called with the
prefix DKH- or ZORA-, and can be combined with the SARC basis sets for the heavier
elements.

DKH-def2-SVP and ZORA-def2-SVP

DKH-def2-SV(P) and ZORA-def2-
SV(P) DKH-def2-TZVP and ZORA-
def2-TZVP
DKH-def2-TZVP(-f) and ZORA-def2-TZVP(-
f) DKH-def2-TZVPP and ZORA-def2-
TZVPP DKH-def2-QZVPP and ZORA-def2-
QZVPP
Minimally augmented versions:
ma-DKH-def2-SVP and ma-ZORA-def2-SVP
ma-DKH-def2-SV(P) and ma-ZORA-def2-
SV(P) ma-DKH-def2-TZVP and ma-ZORA-
def2-TZVP
ma-DKH-def2-TZVP(-f) and ma-ZORA-def2-TZVP(-
f) ma-DKH-def2-TZVPP and ma-ZORA-def2-
TZVPP ma-DKH-def2-QZVPP and ma-ZORA-def2-
QZVPP

The same functionality is offered for the “def” basis sets, e.g. “ZORA-TZVP”. In this
case too, the relativistically recontracted versions refer to the elements H–Kr. To
replicate the behavior of past ORCA versions for elements Rb–I, the prefix “old-” can
be used with these keywords as in the non-relativistic case.

WARNING: Previous verions of ORCA made extensive use of automatic

basis set substitution and aliasing when the use of the DKH or ZORA
Hamiltonians was detected. This is no longer the case! Relativistic versions
of Karlsruhe basis sets now have to be requested explicitly with the
appropriate prefix. SARC basis
sets also have to be requested explicitly.

All-electron Karlsruhe basis sets up to Rn for exact two-component methods (X2C). [4]
The “-2c” variants, e.g. “def2-TZVPall-2c”, are intended for two-component calculations
including spin–orbit coupling. The “-s” variants, e.g. “def2-TZVPall-s”, are augmented
with additional tight functions for NMR shielding calculations. [5] Note that two-
component methods are currently not implemented in ORCA.
x2c-SV(P)all 2c version: x2c-SV(P)all-2c, NMR version: x2c-SV(P)all-s
x2c-SVPall 2c version: x2c-SVPall-2c, NMR version: x2c-SVPall-s
x2c-TZVPall 2c version: x2c-TZVPall-2c, NMR version: x2c-TZVPall-s
x2c-TZVPPall 2c version: x2c-TZVPPall-2c, NMR version: x2c-
TZVPPall-s x2c-QZVPall 2c version: x2c-QZVPall-2c, NMR version: x2c-QZVPall-s
4 6 General Structure of the Input
x2c-QZVPPall 2c version: x2c-QZVPPall-2c,File
NMR version: x2c-
QZVPPall-s
6.3 Basis 5
Sets

SARC basis sets [6–11]

Segmented all-electron relativistically contracted basis sets for use with the DKH2 and
ZORA
Hamiltonians. Available for elements beyond Krypton.
SARC-DKH-TZVP
SARC-DKH-TZVPP
SARC-ZORA-TZVP
SARC-ZORA-
TZVPP
Note: SARC/J is the general-purpose Coulomb-fitting auxiliary for all SARC orbital basis
sets.
SARC2 basis sets for the lanthanides [12]
SARC basis sets of valence quadruple-zeta quality for lanthanides, with NEVPT2-optimized
(3g2h) polarization functions. Suitable for accurate calculations using correlated
wavefunction methods.
SARC2-DKH-QZVP
SARC2-ZORA-
QZVP
Note: Can be called without the polarization functions using ...-QZV. Each basis set has a
large dedicated /JK auxiliary basis set for simultaneous Coulomb and exchange fitting.
Jensen basis sets
pc-n (n = 0, 1, 2, 3, 4) “Polarization-consistent” generally
contracted
basis sets (H–Kr) of up to quintuple-zeta quality, optimized
for SCF calculations
aug-pc-n As above, augmented by diffuse functions
pcseg-n Segmented PC basis sets (H–Kr), DFT-optimized
aug-pcseg-n As above, augmented by diffuse functions
pcSseg-n Segmented contracted basis sets (H–Kr) optimized for
nuclear
magnetic shielding
aug-pcSseg-n As above, augmented by diffuse functions
pcJ-n Segmented contracted basis sets (H–Ar) optimized for spin-
spin
coupling constants
aug-pcJ-n As above, augmented by diffuse functions
Sapporo basis bets
Sapporo-nZP-2012 (n = D, T, Q) All-electron generally contracted non-
relativistic
basis sets (H–Xe)
Sapporo-DKH3-nZP-2012 (n = D, T, Q) All-electron basis sets optimized for the
DKH3
Hamiltonian and finite nucleus (K–Rn)
Correlation-consistent basis sets
cc-pVDZ Dunning correlation-consistent polarized double-zeta
cc-pVTZ Dunning correlation-consistent polarized triple-zeta
cc-pVQZ Dunning correlation-consistent polarized quadruple-zeta
cc-pV5Z Dunning correlation-consistent polarized quintuple-zeta
cc-pV6Z Dunning correlation-consistent polarized sextuple-zeta
6 6 General Structure of the Input
aug-cc-pVnZ
File
(n = D, T, Q, 5, 6) Augmented with diffuse functions
32 6 General Structure of the Input
File

cc-pCVnZ (n = D, T, Q, 5, 6) Core-polarized basis sets

aug-cc-pCVnZ (n = D, T, Q, 5, 6) as above, augmented with diffuse
functions
cc-pwCVnZ (n = D, T, Q, 5) Core-polarized with weighted core
functions aug-cc-pwCVnZ (n = D, T, Q, 5) as above, augmented with diffuse
functions
cc-pVn(+d)Z (n = D, T, Q, 5) with tight d functions
Partially augmented correlation-consistent basis sets [13]
apr-cc-pV(Q+d)Z Augmented with sp diffuse functions on Li–Ca
may-cc-pV(n+d)Z (n = T, Q): sp (T), spd (Q) on Li–Ca
jun-cc-pV(n+d)Z (n = D, T, Q): sp (D), spd (T), spdf (Q) on Li–Ca
jul-cc-pV(n+d)Z (n = D, T, Q): spd (D), spdf (T), spdfg (Q) on Li–Ca
maug-cc-pV(n+d)Z same as jun-, may-, and apr- for n = D, T, and Q,
respectively
DKH versions of correlation-consistent basis sets
cc-pVnZ-DK (n = D, T, Q, 5) Correlation-consistent all-electron basis
sets
for use with the 2nd-order Douglas-Kroll-Hess Hamiltonian
aug-cc-pVnZ-DK (n = D, T, Q, 5) as above, augmented with diffuse
functions cc-pwCVnZ-DK (n = D, T, Q, 5) DK versions of weighted core
correlation-
consistent basis sets
aug-cc-pwCVnZ-DK (n = D, T, Q, 5) weighted-core DK basis sets with
diffuse
functions
cc-pVnZ-DK3 (n = D, T, Q) Correlation-consistent all-electron basis sets
for
lanthanides and actinides with the 3rd-order Douglas-
Kroll-
Hess Hamiltonian
cc-pwCVnZ-DK3 (n = D, T, Q) DK versions of weighted core correlation-
consistent basis sets for lanthanides and actinides
ECP-based versions of correlation-consistent basis sets
cc-pVnZ-PP (n = D, T, Q, 5) Correlation-consistent basis sets
combined with SK-MCDHF-RSC effective core potentials
aug-cc-pVnZ-PP (n = D, T, Q, 5) as above, augmented with diffuse
functions
cc-pwCVnZ-PP (n = D, T, Q, 5) with weighted core functions
aug-cc-pwCVnZ-PP (n = D, T, Q, 5) as above, augmented with diffuse
functions
F12 and F12-CABS basis sets
cc-pVnZ-F12 (n = D, T, Q) Special orbital basis sets for F12
calculations
(larger than the regular D, T, Q-zeta basis sets!)
cc-pCVnZ-F12 (n = D, T, Q) with core polarization functions
cc-pVnZ-PP-F12 (n = D, T, Q) ECP-based versions
cc-pVnZ-F12-CABS (n = D, T, Q) Near-complete auxiliary basis sets for F12
calculations
cc-pVnZ-F12-OptRI (n = D, T, Q) identical to the cc-pVnZ-F12-CABS basis
above cc-pCVnZ-F12-OptRI (n = D, T, Q)
6.3 Basis 33
Sets cc-pVnZ-PP-F12-OptRI (n = D, T, Q)
aug-cc-pVnZ-PP-OptRI (n = D, T, Q,
5) aug-cc-pwCVnZ-PP-OptRI (n = D, T, Q,
5)
Atomic Natural Orbital basis sets
34 6 General Structure of the Input
File

ANO-pVnZ (n = D, T, Q, 5, 6). Our newly contracted ANO basis sets

on
the basis of the cc-pV6Z (or pc-4 where missing) primitives.
These are very accurate basis sets that are significantly
better than the cc-pVnZ counterparts for the same number
of basis functions (but much larger number of primitives of
course).
saug-ANO-pVnZ (n = D, T, Q, 5) augmentation with a single set of sp
functions.
Greatly enhances the accuracy of the SCF energies but not
for correlation energies.
aug-ANO-pVnZ (n = D, T, Q, 5) full augmentation with spd, spdf, spdfg
set of
polarization functions. Almost as expensive as the next
higher basis set. In fact, aug-ANO-pVnZ = ANO-pV(n +
1)Z with the highest angular momentum polarization
function deleted.
Relativistic contracted ANO-RCC basis sets
ANO-RCC-FULL The complete ANO-RCC basis sets (H-Cm). Some default
contractions are provided for convenience with the
keywords:
ANO-RCC-
DZP ANO-
RCC-TZP
ANO-RCC-
QZP
Miscellaneous and specialized basis sets
D95 Dunning’s double-zeta basis set (H–Cl).
D95p Polarized version of D95.
MINI Huzinaga’s minimal basis set.
MINIS Scaled version of the MINI.
MIDI Huzinaga’s valence double-zeta basis set.
MINIX Combination of small basis sets by Grimme (see Table 9.7).
Wachters+f First-row transition metal basis set (Sc–Cu).
Partridge-n (n = 1, 2, 3, 4) Uncontracted basis sets by Partridge.

LANL2DZ Los Alamos valence double-zeta with Hay–Wadt ECPs.

LANL2TZ Triple-zeta version.
LANL2TZ(f) Triple-zeta plus polarization.
LANL08 Uncontracted basis set.
LANL08(f) Uncontracted basis set + polarization.

EPR-II Barone’s basis set (H, B–F) for EPR calculations (double-
zeta).
EPR-III Barone’s basis set for EPR calculations (triple-zeta).
IGLO-II Kutzelnigg’s basis set (H, B–F, Al–Cl) for NMR and EPR
calculations.
IGLO-III Larger version of the above.
aug-cc-pVTZ-J Sauer’s basis set for accurate hyperfine coupling constants.

Auxiliary basis sets. Auxiliary basis sets for the RI-J and RI-MP2 approximations can also be
6.3 Basis 35
Sets
specified directly in the simple input:
36 6 General Structure of the Input
File

Table 6.4: Overview of auxiliary basis sets available in ORCA.

Auxiliary basis sets for Coulomb fitting
Def2/J Weigend’s “universal” Coulomb fitting basis that is suitable
for
all def2 type basis sets. Assumes the use of ECPs beyond Kr
SARC/J (do
not use with DKH/ZORA).
General-purpose Coulomb fitting basis set for all-electron
calcula- tions. Consists of the decontracted def2/J up to Kr
and of our own auxiliary basis sets for the rest of the periodic
table. Appropriate
for use in DKH or ZORA calculations with the recontracted
x2c/J
ver- sions of the all-electron def2 basis sets (up to Kr) and the
SARC basis sets for the heavier elements.
Weigend’s Coulomb fitting basis for the all-electron x2c-
XVPall basis sets.
Auxiliary basis sets for simultaneously fitting Coulomb and exchange
Fitting basis sets developed by Weigend for fitting simultaneously Coulomb and exchange
energies. They are quite large and accurate. They fit SCF energies very well but even if they are
large they
do not fit correlation as well as the dedicated “/C” auxiliary basis sets.
Def2/JK Coulomb+Exchange fitting for all def2 basis sets
Def2/JKsmall reduced version of the above
cc-pVnZ/JK (n = T, Q, 5) for the respective cc-pVnZ orbital basis
aug-cc-pVnZ/JK (n = T, Q, 5) for the respective aug-cc-pVnZ orbital basis
Auxiliary basis sets for correlation calculations
Def2-SVP/C Correlation fitting for the def2-SVP orbital basis
Def2-TZVP/C for the def2-TZVP orbital basis
Def2-TZVPP/C for the def2-TZVPP orbital basis
Def2-QZVPP/C for the def2-QZVPP orbital basis
Def2-SVPD/C for the def2-SVPD orbital basis
Def2-TZVPD/C for the def2-TZVPD orbital basis
Def2-TZVPPD/C for the def2-TZVPPD orbital basis
Def2-QZVPPD/C for the def2-QZVPPD orbital basis
cc-pVnZ/C (n = D, T, Q, 5, 6) for the respective cc-pVnZ orbital basis
aug-cc-pVnZ/C (n = D, T, Q, 5, 6) for the respective aug-cc-pVnZ orbital
basis
cc-pwCVnZ/C (n = D, T, Q, 5) for the respective cc-pwCVnZ orbital basis
aug-cc-pwCVnZ/C (n = D, T, Q, 5) for the respective aug-cc-pwCVnZ orbital
basis
cc-pVnZ-PP/C (n = D, T, Q) for the respective cc-pVnZ-PP orbital basis
aug-cc-pVnZ-PP/C (n = D, T, Q) for the respective aug-cc-pVnZ-PP orbital basis
cc-pwCVnZ-PP/C (n = D, T, Q) for the respective cc-pwCVnZ-PP orbital basis
aug-cc-pwCVnZ-PP/C (n = D, T, Q) for the respective aug-cc-pwCVnZ-PP orbital
basis
cc-pVnZ-F12-MP2fit (n = D, T, Q) for the respective cc-pVnZ-F12 orbital basis
cc-pCVnZ-F12-MP2fit (n = D, T, Q) for the respective cc-pCVnZ-F12 orbital basis
cc-pVnZ-PP-F12-MP2fit (n = D, T, Q) for the respective cc-pVnZ-PP-F12 orbital basis
AutoAux Automatic construction of a general purpose auxiliary basis for
simultaneously fitting Coulomb, exchange and correlation
calcula- tions. See section 9.5.2 for details.
6.3 Basis 37
Sets

NOTE: ORCA versions before 4.0 allowed the use of multiple keywords to invoke the same def2
Coulomb or Coulomb+exchange fitting basis set of Weigend. To avoid confusion all these keywords
are now deprecated and the auxiliary basis sets are simply called using “def2/J” and “def2/JK”.

NOTE: Starting from version 4.1 ORCA internally stores up to five basis sets for each calculation:
the obligatory orbital basis set; an AuxJ Coulomb-fitting basis for the RI-J, RIJDX/RIJONX, and
RIJCOSX approximations; an AuxJK Coulomb- and exchange-fitting basis used for RIJK; an AuxC
auxiliary basis for the RI approximation in dynamical electron correlation treatments (such as RI-
MP2, RI-CCSD, and
DLPNO methods); and a complementary auxiliary basis set (CABS) for F12 methods. “/J” basis sets
given in the simple input are assigned to AuxJ and likewise for the other types. Non-standard
assignments like AuxJ="def2/JK" are possible only through the %basis block input (see section 9.5.1).

6.3.2 Use of scalar relativistic basis sets

For DKH and ZORA calculations ORCA provides relativistically recontracted versions of the Karlsruhe
basis sets for elements up to Kr. These can be requested by adding the prefix DKH- or ZORA- to the
normal basis set name. Note that for other non-relativistic basis sets (for example Pople-style bases) no
recontraction has
been performed and consequently such calculations are inconsistent! The basis set and the scalar
relativistic Hamiltonian are specified in the keyword line, for example:

! B3LYP ZORA ZORA-TZVP ...

If an auxiliary basis set is required for these recontracted Karlsruhe basis sets, we recommend the use
of the decontracted def2/J. This can be obtained simply by using the keyword “! SARC/J” (instead of
the equivalent “! def2/J DecontractAuxJ”) and is the recommended option as it simultaneously
covers the use of SARC basis sets for elements beyond Krypton.

! TPSS ZORA ZORA-def2-TZVP SARC/J ...

For all-electron calculations with elements heavier than Krypton we offer the SARC (segmented all-
electron relativistically contracted) basis sets [6–11]. These were specifically developed for scalar
relativistic calculations and are individually adapted to the DKH2 and ZORA Hamiltonians. In this case
the Coulomb-fitting auxiliary basis set must be specified as SARC/J, or alternatively the AutoAux
keyword (9.5.2) can be employed to create auxiliary basis sets.

! PBE DKH SARC-DKH-TZVP SARC/J ...

Specifically for wavefunction-based calculations of lanthanide systems we recommend the more heavily
polarized SARC2 basis sets [12].

Other basis sets suitable for scalar relativistic calculations are various versions of the all-electron
correlation- consistent basis sets that are optimized for the DKH2 Hamiltonian and can be called with
the suffix ”-DK”. The relativistically contracted atomic natural orbital (ANO-RCC) basis sets of Roos
and coworkers were also developed for the DKH2 Hamiltonian and have almost complete coverage of
the periodic table (up to Cm).