4.2 The Atomic Attributes Menu

After you specified the molecular geometry and symmetry and wrote this data to file, you will encounter the atomic attributes menu, which is the second of the four main menus. You will enter this menu, if all necessary data cannot be read from your input file or if you do not use an input file. This menu deals with the specification of basis sets and other data related to the atom type:

 ATOMIC ATTRIBUTE DEFINITION MENU  ( #atoms=5     #bas=5     #ecp=0     )  
 
 b    : ASSIGN ATOMIC BASIS SETS  
 bb   : b RESTRICTED TO BASIS SET LIBRARY  
 bl   : LIST ATOMIC BASIS SETS ASSIGNED  
 bm   : MODIFY DEFINITION OF ATOMIC BASIS SET  
 bp   : SWITCH BETWEEN 5d/7f AND 6d/10f  
 lib  : SELECT BASIS SET LIBRARY  
 ecp  : ASSIGN EFFECTIVE CORE POTENTIALS  
 ecpb : ecp RESTRICTED TO BASIS SET LIBRARY  
 ecpi : GENERAL INFORMATION ABOUT EFFECTIVE CORE POTENTIALS  
 ecpl : LIST EFFECTIVE CORE POTENTIALS ASSIGNED  
 ecprm: REMOVE EFFECTIVE CORE POTENTIAL(S)  
 c    : ASSIGN NUCLEAR CHARGES (IF DIFFERENT FROM DEFAULTS)  
 cem  : ASSIGN NUCLEAR CHARGES FOR EMBEDDING  
 m    : ASSIGN ATOMIC MASSES (IF DIFFERENT FROM DEFAULTS)  
 dis  : DISPLAY MOLECULAR GEOMETRY  
 dat  : DISPLAY ATOMIC ATTRIBUTES YET ESTABLISHED  
 h    : EXPLANATION OF ATTRIBUTE DEFINITION SYNTAX  
 *    : TERMINATE THIS SECTION AND WRITE DATA OR DATA REFERENCES TO control  
 GOBACK=& (TO GEOMETRY MENU !)

The headline gives you the number of atoms, the number of atoms to which basis sets have already been assigned and the number of atoms to which effective core potentials have already been assigned. Most of the commands in this menu deal with the specification of basis sets and pseudopotentials.

Basis sets available

The following basis sets are available on $TURBODIR/basen/, which you may inspect to see which other basis sets are supported automatically. The corresponding publications can be found here 1.3.

SV(P) or def-SV(P)

for routine SCF or DFT. Quality is about 6–31G*.

TZVP or def-TZVP

for accurate SCF or DFT. Quality is slightly better than 6–311G**.

TZVPP or def-TZVPP

for MP2 or close to basis set limit SCF or DFT. Comparable to 6–311G(2df).

QZVP and QZVPP

for highly correlated treatments; quadruple zeta + 3d2f1g or 4d2f1g (beyond Ne), 3p2d1f for H.

These basis sets are available for atoms H–Kr, and the split-valence (SV) and valence-triple-ζ (TZV) basis sets types with ECPs also for Rb–Rn, except lanthanides.

For calculations with the programs ricc2, ccsdf12, and pnoccsd optimized auxiliary basis sets are available for the basis sets SV(P), SVP, TZVP, TZVPP, and QZVPP.

NEW: New sets of basis functions, partly identical with those mention above, denoted def2-XYZ are available for atoms H–Rn [6]. The def2 basis sets for 5p and 6p block elements are designed for small core ECPs (ECP-28, ECP-46 and ECP-60). For each family, SV, TZV, and QZV, we offer two sets of polarisation functions leading to:

def2-SV(P) and def2-SVP

def2-TZVP and def2-TZVPP

def2-QZVP and def2-QZVPP

We strongly recommended the new def2-basis, since they have been shown to provide consistent accuracy across the periodic table.

Recommendation

Use the same basis set type for all atoms; use ECPs beyond Kr since this accounts for scalar relativistic effects.

New basis sets (def2-XYZ): MP2 implies RI-MP2 and RICC2

exploratory

MP2: SVP

almost quantitative

DFT: SV(P), HF: SVP, MP2: TZVPP; properties (HF and DFT): TZVPP

quantitative

DFT: TZVP, HF: TZVPP, MP2: QZVPP

basis set limit

DFT: QZVP, HF: QZVP

If you want a better basis than SV(P), assigned automatically, use b all def2-TZVP (or another basis). The assignment can be checked by bl.

Diffuse functions should only be added if really necessary. E.g. for small anions or treatment of excited states use: TZVP instead of SVP + diffuse. This is more accurate and usually faster. Only for excited states of small molecules or excited states with (a partial) Rydberg character add additional diffuse functions (e.g. by using the aug-cc-pVTZ basis) as well as the keyword diffuse, for more information, see page 706 in the keyword section.

[Old basis sets (def-XYZ): For standard correlated calculations (MP2, RI-MP2, RI-CC2) use the doubly-polarized TZVPP (or def-TZVPP) basis.]

Correlation-Consistent (Dunning) Basis Sets

Dunning basis sets like cc-pVDZ, cc-pVTZ, cc-pVQZ are also supported, e.g. by b all cc-pVTZ. But these basis sets employ generalized contractions for which TURBOMOLE is not optimized. This has in particular strong effects on the performance of all programs which use 4-index electron repulsion integrals, for RI-MP2 and RI-CC2 this is partially compensated by the RI-approximation.

The following correlation consistent basis sets are available in the TURBOMOLE basis set library:

cc-pVXZ

standard valence X-tuple zeta basis sets (X = D, T, Q, 5, 6); available for H, He, Li–Ne, Na–Ar, K, Ca, Ga–Kr.
(cc-pV6Z only for H, He, B–Ne, Al–Ar; for Al–Ar also the recommended newer cc-pV(X+d)Z sets are available)

cc-pwCVXZ-PP 

weighted core-valence x-tuple zeta basis sets (X= D, T, Q, 5) are available for post-d main group elements Ga–Kr, In–Xe, and Tl–Rn. (also pure valence basis sets cc-pVXZ-PP are available for these elements, but it is not recommended to use them)

cc-pwCVXZ

weighted core-valence X-tuple zeta basis sets (X = D, T, Q, 5); available for B–Ne, Al–Ar, and Ga–Kr
(for Al–Ar also the recommended combination of the cc-pV(X+d)Z sets with the core valence functions (wC), i.e. the cc-pwCV(X+d)Z basis set are available)

aug-

diffuse functions for combination with the basis sets cc-pVXZ, cc-pV(X+d)Z, cc-pwCVXZ, cc-pV(X+d)Z, cc-pVXZ-PP or cc-pwCVXZ-PP; available for H, He, B–Ne, Al–Ar with X = D–6 and Ga–Kr, In–Xe, and Tl–Rn with X = D–5.

cc-pVXZ-F12

with X = D, T, Q for use with the explicitly-correlated F12 variants of wavefunction methods (MP2-F12, CCSD(F12*), etc.)

For calculations with the programs that employ the RI approximation with a correlated wavefunction optimized auxiliary basis sets are available for most of the correlation consistent basis set series.

4.2.1 Description of the commands

b

With b you can specify basis sets for all atoms in your molecule. After entering b you will be asked to specify the atoms to which you want to assign basis sets. You can do this in the usual ways (refer to Section 4.0.4), including all and none. Then you will be asked to enter the nickname of the basis set to be assigned. There are two principal ways to do this:

You can switch between the two modes with ‘+’ (switches to append mode) and ‘-’ (switches to non-append mode).

Once you have specified your basis set nickname, define will look in the standard input file (normally control) for this basis set. If it can not be found there, you can switch to the standard basis set library (if you did not use a standard input file, the standard library will be searched immediately). If the basis set cannot be found there, you are asked either to enter a new standard library (which will be standard only until you leave this menu) or another input file, where the basis set can be found. If you do not know the exact nickname of your basis set, you may abbreviate it by ‘?’, so you could enter h DZ? to obtain basis sets like h DZ, h DZP, h DZ special, etc. define will give you a list of all basis sets whose nicknames match your search string and allows you to choose among them. You may also use the command list to obtain a list of all basis sets cataloged.

bb

bb does essentially the same as b but does not search your default input file for basis sets. Instead it will look in the basis set library immediately.

bl

bl gives you a list of all basis sets assigned so far.

bm

This command is used to modify basis sets which are already assigned. The corresponding submenu is self-explanatory, but we recommend to change directly the file basis.

bp

The TURBOMOLE programs normally work with basis sets of 5d-functions (which means they delete the s-component of the full 6d-set). bp allows to switch between the proper 5d/7f -set and the Cartesian 6d/10f -set.

ecp

This command allows you to specify effective core potentials for some atoms. The assignment works exactly like the specification of basis sets (see above).

ecpb

This one does the same as command ecp, but restricted to the basis set library (the input file will not be used).

ecpi

ecpi gives you some general information about what type of pseudopotentials is supported. For more information we refer to [29] and references therein.

ecpl

ecpl gives you a list of all pseudopotentials assigned so far.

ecprm

ecprm allows to remove a pseudopotential assignment from the list. This command is useful if you want to perform an all electron calculation after an ECP treatment.

c

Command c assigns a special nuclear charge to an atom. This is useful to define dummy centers for counterpoise calculations where you set the nuclear charge to zero.

m

This command allows you to assign non-default atomic masses to an atom. Use this if you want to analyze isotopic shifts of calculated harmonic frequencies. The standard masses are those of the natural isotope mix.

dat

dat gives you a list of all data already specified.

*

This is again the usual command to leave a menu and write all data to file control (or any other output file). It is not possible to leave this menu unless basis sets have been specified for all atoms in your molecule. If you do not want to use a basis set for one or more atoms, use the basis set nickname none. On leaving this menu, the data groups $atoms and $basis will be written to the output file.

After you finished this menu, you will enter the third main menu of define which deals with start vectors and occupation numbers.