Keywords for Modules DSCF and RIDFT

`$denconv`*real*-

Convergency criterion for the root mean square of the density matrix. If you want to calculate an analytical MP2 gradient (program`mpgrad`)*real*should be 1.d-7 or less. `$dft`*options*-

Listing of all possible sub-keywords for`$dft`

(cross-references are given).The user normally has to choose only the functional and the grid size, see below. All other parameters have proven defaults.

`functional`*name*-

Specification of the functional, default is BP86, printed as`functional b-p`. For all possible--and useful--functionals, please refer to page and for definition of the functionals the section 6.2 on page .Example (default input):

$dft functional b-p

`gridsize`*integer*or`m`*integer*-

Specification of the spherical grid (see section 15.2.5 on page ). Default is`gridsize m3`.Example:

$dft gridsize m3

`gridtype`*integer*- --not recommended for
use--

Specification of the mapping of the radial grid.Possible values for

`gridtype`are 1,…, 6, but`gridtype 4`to`6`is only for the use with`functional lhf`(see page ). For the definition of`gridtype 1`-`3`, please refer to Eq. (16), (17) and, (19) in Ref. [131].Example (default value):

$dft gridtype 3

`debug`*integer*-

Flag for debugging.`debug 0`means no debug output (default),`debug 1`means some output,`debug 2`means a lot more output. Be careful! `nkk`*integer*-

Specification of the sharpness of the partition function as proposed by Becke [132], default is`nkk 3`. The usage of`nkk`makes sense only in the range 1≤`nkk`≤6.Example:

$dft nkk 3

- --not
recommended for use--

Only for user-specified Lobatto grids, i.e.`gridsize 9`,`ntheta`specifies the number of*θ*points and`nphi`specifies the number of*φ*points. For the fixed Lobatto grid, i.e.`gridtype 8`, the default value is`ntheta 25`and`nphi 48`.When

`gridsize 9`is given, you have to specify both,`ntheta`and`nphi`(see below), otherwise the program will crash. The restriction for user-defined Lobatto grids is the number of grid points, which must not exceed 2000 grid points.Example:

$dft gridsize 9 ntheta 30 nphi 60

`old_RbCs_xi`-

Original grids had not been carefully optimized for all atoms individually. This has now been done, which let to changes of*ξ*for Rb and Cs only resulting in minor improvements. If you have ongoing projects, which have been started with the old grids, you should continue using them with the keyword`old_RbCs_xi`.Example:

$dft old_RbCs_xi

`radsize`*integer*-

Specifies the number of radial grid points. Default values depend on type of atom and grid (see keyword`gridsize`). The formula for the radial gridsize is given as,number of radial grid points = ioffrad + ( radsize -1)*5 .

ioffrad is atom-dependent, the more shells of electrons, the larger ioffrad:

elements ioffrad elements ioffrad for H-He 20 for K-Kr 40 for Li-Ne 25 for Rb-Xe 45 for Na-Ar 30 for Cs-Lw 50

The radial grid size increases further for finer grids:

`gridsize`1 2 3 4 5 6 7 8 9 `radsize`1 2 3 6 8 10 14 9 3

If you want to converge results with respect to radial grid size, increase

`radsize`in steps of 5, which is convenient (see equation above).

`diffuse`*integer*-

Serves to increase quadrature grids; this is recommended in case of very diffuse wavefunctions. With the keyword`diffuse`grids are modified by changing the linear scaling factor*ξ*of radial grid points and the radial gridsize:

`radsize``radsize`+*incr**ξ**ξ***scal*

`diffuse`*integer*1 2 3 4 5 6 *incr*1 2 3 4 5 6 *scal*1.5 2.0 2.8 4.0 5.0 6.0

For information about the linear scaling parameter

*ξ*, see Eq. (16)-(19) and Table 1 in Ref. [131].In addition, the reduction of spherical grid points near nuclei is supressed, i.e.

`fullshell on`is set (see page ).Note: the keyword

`radsize`*integer*overrules the setting of*incr*; for more information, see p. .

Recommendation: For diffuse cases use

`gridsize m4`(or larger) in combination with`diffuse 2`and check the number of electrons; for more difficult cases use`diffuse 4`. In case of doubt, verify the calculation with a larger grid, i.e.`gridsize 7`.The test suite example

`$TURBODIR/TURBOTEST/dscf/short/H3PO4.DSCF.DIFFUSE`provides an example of usage; this also gives reasonable values for damping and orbitalshift to reach convergence in this and similar cases, see`$scfdamp`and`$scforbitalshift`(p. and p. ).Example (Recommendation):

$dft gridsize m4 diffuse 2

- --for
developers only--

Radial grid points have a linear scaling parameter*ξ*, see Eq.(16)-(19) and Table 1 in Ref. [131]. With the following input,$dft rhostart 50 rhostop 200

one performs a numerical integration for the density and the exchange correlation term for*ξ*= 0.5,(0.01), 2.0 for given MOs and functional. NOTE: only molecules with a single atom type can be used. The results serve to establish stable, optimal*ξ*values, see Figure 1 in Ref. [131]. Program stops after this testing. `reference`-

Usage of the reference grid, which is a very fine grid with very tight thresholds. The default values for the different variables are:gridsize 7 radsize 14 fullshell 1 dgrenze 16 fgrenze 16 qgrenze 16 fcut 16

Please refer to the corresponding sub-keywords for explanation.If you want to use the reference grid, you have to skip the keyword

`gridsize`, and type instead`reference`. Example:$dft functional b-p reference

`test-integ`-

Check if the selected grid is accurate enough for the employed basis-set by performing a numerical integration of the norm of all (occupied and virtual) orbitals. Useful for LHF. . `batchsize`*integer*-

Grid points are sorted into batches, which are then processed. This increases efficency. This should be changed only by developers. Default is`batchsize 100`. `fullshell`-

Standard grids have reduced number of spherical grid points near nuclei. With the keyword`fullshell`this reduction is suppressed. Reference grid (see keyword`reference`) always has full spherical grids with 1202 points. Should be used to checked the influence of spherical grid reduction.Example for the usage of

`fullshell`:$dft functional b-p gridsize m4 fullshell

- --for
developers only--

Values of real effects efficiency of the quadrature, default is`symblock1 0.001`and`symblock2 0.001`, one can try higher or smaller values. `xparameter`*integer*- --not recommended for
use--

Where`xparameter`(default) can be:`sgrenze`(8),`fgrenze`(10),`qgrenze`(12),`dgrenze`(12) and,`fcut`(14). These parameters control neglect of near zeros of various quantities. With`xparameter`*integer*one changes the default.*integer*larger than defaults will increase the numerical accuracy. Tighter threshold are set automatically with keyword`$scfconv`(see section 15.2.5 on page ). `weight derivatives`-

Includes the derivatives of quadrature weights to get more accurate results. Default is that the derivatives of quadrature weights will be not considered, see section 15.2.8 on page . `gridordering`-

Grid points are ordered into batches of neighbouring points. This increases efficiency, since now zeros can be skipped for entire batches.`gridordering`is default for serial version, not for the parallel one. You cannot use`weight derivatives`and`gridordering`together.Example for switching off

`gridordering`:$dft gridordering 0

`$electrostatic field`-

Specification of external electrostatic field(s). The specification may take place either by`Ex, Ey, Ez`

or by`x, y, z, |E|`

. See also`$fldopt`.Example:

$electrostatic field 0.1000E-03 0.000 0.000

`$fermi``tmstrt=<300.0> tmend=<100.0> tmfac=<0.9> hlcrt=<1.0E-01> stop=<1.0E-03> nue=<N>`-

Requests calculation of occupation numbers at a finite temperature*T*. For an orbital with the energy the occupation number*n*_{i}∈0, 1 is calculated as*n*_{i}= erfc,*μ*is the Fermi level. The factor*f*= 4*k*/ is chosen to yield the same slope at the Fermi level as the Fermi distribution.Calculation of the fractional occupation numbers starts when the current HOMO-LUMO gap drops below the value given by

`hlcrit`(default: 0.1). The initial temperature given by`tmstrt`(default: 300K) is reduced at each SCF cycle by the factor`tmfac`(default: 1.0) until it reaches the value`tmend`(default: 300K). Note that the default values lead to occupation numbers calculated at a constant*T*= 300K. Current occupation numbers are frozen if the energy change drops below the value given by`stop`(default: 1 ⋅10^{-3}). This prevents oscillations at the end of the SCF procedure.Calculation of fractional occupation numbers often requires much higher damping and orbital shifting. Please adjust the values for

`$scfdamp`and`$scforbitalshift`if you encounter convergence problems.In UHF runs this option can be used to automatically locate the lowest spin state. In order to obtain integer occupation numbers

`tmend`should be set to relatively low value, e.g. 50K.Calculation of fractional occupation numbers should be used only for single point calculations. When used during structure optimizations it may lead to energy oscillations.

The optional

`nue`value (number of unpaired electrons) can be used to force a certain multiplicity in case of an unrestricted calculation.`nue=0`is for singlet,`nue=1`for dublet, etc. `$firstorder`-

Perform first-order SCF-calculation, i.e. perform only one SCF-iteration with the start MOs (which should be the orthogonalized MOs of two independent subsystems as is explained in detail in Chapter 13). `$fldopt`*options*-

Specification of options related with external electrostatic fields. The following options are available:`1st derivative on/off`-

Calculate numerical 1st derivative of SCF energy with respect to electrostatic field (default: off), increment for numerical differentiation is`edelt`(see below). `2nd derivative on/off`-

Calculate numerical 2nd derivative of SCF energy with respect to electrostatic field (default: off), increment for numerical differentiation is edelt. `edelt=`*real*-

Increment for numerical differentiation (default: 0.005). `fields on/off`-

Calculate SCF energy for non-zero external electrostatic

fields defined in`$electrostatic field`. `geofield on/off`-

Calculate SCF energy for one external field definition and dump disturbed MOs onto`$scfmo`

. This enables to evaluate properties or perform geometry optimizations in the presence of an external field.

**Caution**: don't use the RI approximation for all these calculations since this will lead to non-negligible errors!! `$incore`*integer*-

By using this option the two-electron integrals are kept in RAM;*integer*specifies how many megabytes should be allocated. If the integrals exceed the RAM allocated the program reverts to the standard mode. Supports all methods which process two-electron integrals, i.e. SCF and DFT (including hybrid functionals); RHF and UHF.The following condition must be met:

and rhfshells 1 or 2. It is advisable to set

`$thize`

as small as possible (e.g.`$thize``0.1d-08`

) and to remove the keyword`$scfdump`.

**Note**: this keyword does not work for parallel runs. `$mo-diagram`*only*`nirreps=`*integer*-

If this keyword is set the energies and symmetry labels of all occupied MOs will be dumped to this data group. This may be helpful to draw mo-diagrams. If*only*has been set only the start MOs are dumped and the program quits.`nirreps`will hold the total number of displayed orbitals after the successful run. `$moprint`-

If this keyword is present all occupied orbitals are dumped to standard output. Be careful about this option as it can create huge output files in case of many basis functions. `$mo output format`*format*-

If this line is present, the dscf program is forced to output the MOs using the new FORTRAN format*format*regardless of the*format*-option in data group`$scfmo`. Otherwise the input format will be used.Example:

`$mo output format(3(2x,d15.8))`

`$natural orbitals`-

This data group will be written after an UHF calculation (together with $natural orbital occupation) and contains the natural space orbitals (same syntax as`$scfmo`). `$natural orbital occupation`-

This data group will be written after an UHF calculation (together with`$natural orbitals`) and contains the occupation of natural orbitals (syntax as any data group related with orbital occupation information, e.g.`$closed shells`), e.g.a 1-5 ( 2.00000000000000 ) a 6 ( 1.99949836999366 ) a 7 ( 1.99687490286069 ) a 8 ( 1.00000000000000 ) a 9 ( .00312509713931 ) a 10 ( .00050163000634 )

`$point_charges`-

Specification of position and magnitude of point charges to be included in the Hamiltonian. Each point charge is defined in the format<x> <y> <z> <q>

with, , being the coordinates and its charge,e.g.

$point_charges thr=<real> self-energy list 2. 2. 2. 5. 5. 0. 0. 2.5

In addition the following optional arguments may be given:`thr`- distance threshold for discarding redundant point charges,
default value 10
^{-6}. `selfenergy`- if given, the selfenergy of the point charge array will will be included in the energy and the gradient
`list`- print all point charges in the output (default is to print the point charges only if less than 100 charges given)

`$prediag`

concerns the first SCF iteration cycle if start MOs from an EHT guess are used.The SCF iteration procedure requires control mechanisms to ensure (fast) convergence, in

`TURBOMOLE`these are based on orbital energies*ε*_{i}of the preceeding iteration used for level shifting and damping (besides DIIS, see below). This feature cannot be used in the first iteration if EHT MOs are employed as start, since*ε*_{i}are not available. The keyword`$prediag`provides '*ε*_{i}of the zeroth iteration' by diagonalization of occ-occ and virt-virt part of the first Fock matrix, to allow for level shifting etc.. See`$scfdiis`below.`$restart dscf`*twoint*

Try a`dscf`restart. The program will read the data group`$restartd`(which must exist, also`$scfmo`has to exist!) and continue the calculation at the point where it ended before. If the additional option`twoint`

is appended, the program will read the two-electron integrals from the files specified in`$scfintunit`, so there will be almost no loss of cpu-time.All this information is normally provided by the previous

`dscf`run if the keyword`$scfdump`(see there) was given.`$restartd`*data*

Data provided by a previous dscf run that has been interrupted. This keyword is created when`$scfdump`was given.`$rundimensions`*data*

is set by define so usually no changes are necessary. The dimensions must be greater or equal to those actually required, i.e. you can delete basis functions and keep rundimensions. This keyword is not necessary for small cases.

Example:dim(fock,dens)=6072 natoms=6 nshell=34 nbf(CAO)=108 nbf(AO)=98 dim(trafo[SAO<-->AO/CAO])=256 rhfshells=1

`$scfconv`*integer*

SCF convergency criterion will be 10^{-integer}for the energy. Gradients will only be evaluated if*integer*> 6.`$scfdamp start=<.500> step=<.050> min=<.100>`

Damping parameters for SCF iterations in order to reduce oscillations. The old Fock-operator is added to the current one with weight 0.5 as*start*; if convergence is good, this weight is then reduced by the*step*0.05 in each successive iteration until the*min*imum of 0.1 is reached. (These are the default settings of define for closed-shell RHF). DSCF automatically tries to adjust the weight to optimize convergence but in difficult cases it is recommended to start with a large weight, e.g. 1.5, and to set the minimum to a larger value, e.g. 0.5.`$scfdebug`*options*

Flags for debugging purposes. Following options are available:`vectors`*integer*-

Output level concerning molecular orbitals.*integer*=0 (default) means minimal output, >1 will output all start MOs and all MOs in each iteration. `density`*integer*-

Output level concerning difference density matrices. `debug`*integer*-
*integer*> 0 will dump a lot of information--be careful!

`$scfdenapproxl`*integer*

Direct SCF procedures build the Fock matrix by exploiting information from previous iterations for better efficiency. With this keyword information from the last*integer*iterations will be used. This feature is switched on with the default value 20, even if the keyword is absent. The user may reduce the number of iterations employed to smaller values (e.g. 10) in cases were numerical stability could become an issue. With the value 0 this feature is switched off; the Fock matrix is constructed from scratch in each iteration.`$scfdiis`*options*

Control block for convergence acceleration via Pulay's DIIS^{}.

Options are:`errvec=`*char*- specifies the
kind of error vector to be used (two different kind of DIIS
algorithms)
*char*`='FDS' or 'SDF' or 'FDS-SDF'`-

uses (*FDS*-*SDF*) as error vector. *char*`= none`-

no DIIS *char*`= sFDs`-

use*S*^{-1/2}*FDS*^{1/2}- transposed

`maxiter=`*integer*-

maximum number of iterations used for extrapolation. `debug=`*integer*-

debug level (default: 0)`integer=1`- print applied DIIS coefficients
`integer=2`- print DIIS matrix and eigenvalues, too

`qscal=`*real*-

scaling factor in DIIS procedure:`qscal`> 1 implies some damping,`qscal`= 1.0: straight DIIS. `thrd=`*real*-

directs the reduction of qscal to`qscal`= 1.0 (no damping in DIIS), done if ||*errvec*|| <`thrd`.

`$prediag`(see above) and`$scfdiis``errvec=FDS-SDF`,`maxiter=5`,`qscal=1.2`,`thrd=0.0`, this implies DIIS damping in all iterations, prediag is switched of.Recommended:

`errvec=sFDs`leads to the following defaults:`qscal=1.2`, for SCF runs:`maxiter=6`and`thrd=0.3`, prediag is off; for DFT runs:`maxiter=5`and`thrd=0.1`prediag is on. If you want to switch off prediag put`$prediag none`.`$scfdump`

Dump SCF restart information onto data group`$restartd`and dump SCF MOs in each iteration onto`$scfmo`(scfdump = iter). Additionally, a data block`$scfiterinfo`will be dumped containing accumulated SCF total-, one- and two-electron energies of all previous SCF iterations. Information that will allow you to perform a restart if your calculation aborts will be dumped on data group`$restartd`(see also`$restart`).`$scfintunit`*options*

Disc space specification for two-electron integrals. The following suboptions are available (and necessary):`unit=`*integer*-

Fortran unit number for this file. Unit numbers 30,31,... are recommended. `size=`*integer*-

Filespace in megabytes for this file.`size=0`leads to a fully direct run.`size`is set by a statistics run, see`$statistics`. DSCF switches to direct mode if the file space is exhausted. `file=`*char*-

Filename. This may also be a complete path name, if you want to store the integrals in a special directory. Make sure the file is local, otherwise integrals are transmitted over the network.

`$scfintunit`may look like this:$scfintunit unit=30 size=35 file=twoint1 unit=31 size=35 file=/users/work/twoint2

Maximal 30 files may be specified in this way.`$scfiterlimit`*integer*

Maximum number of SCF iterations (default: 30).`$scfmo`*none*`file=`*char*

Input/output data group for SCF MOs. You can specify`none`-

To perform a calculation without a start vector (i.e. use a core Hamiltonian guess). `file=`*char*-

The file where the MOs are written on output (default: mos).

These two options can also be used for

`$uhfmo_alpha`and`$uhfmo_beta`to use a core guess and write the molecular orbitals to`file`

.After running

`define`or a`TURBOMOLE`calculation additional options may appear specifying the origin of the MOs:`expanded`-

These MOs were obtained by projection form another basis set. They should not be used for wavefunction analysis. `scfconv=`*integer*-

The MOs are converged SCF MOs , the convergence criterion applied was 10^{-integer} `scfdump=`*integer*-

The MOs are unconverged SCF MOs which were written on this data group after iteration*integer*. The latter three options are mutually exclusive. `format`*(format string)*-

This specifies the FORTRAN format specification which was used for MO output. The standard format is (4d20.14). (See data group`$mo output format`.)

Example:

Your data group`$scfmo`could look like this after a successful`TURBOMOLE`run :$scfmo scfconv=7 format(3(1x,d19.13)) 1 a1 eigenvalue=-.524127 nsao=6 .1234567890123d+01 -.1234567890123d+00 .1234567890123d-01 .1234567890123d+01 -.1234567890123d+00 3 a2 eigenvalue=-.234810 ...

`$scforbitalorder on/off`

Order SCF MOs with respect to their energies (default: on)`$scforbitalshift`*options*

To assist convergence, either the energies of unoccupied MOs can be shifted to higher energies or, in open-shell cases, the energies of closed-shell MOs to lower energies. In general a large shift may help to get better convergence.Options are:

`noautomatic`-

Automatic virtual shell shift switched off. `automatic`*real*-

Automatic virtual shell shift switched on; the energies of virtual orbitals will be shifted if the HOMO-LUMO gap drops below*real*such that a gap of*real*is sustained. This is the default setting if the keyword is missing with*real*=0.1. `closedshell=`*real*-

Option for open-shell cases. Closed shells are shifted to lower energies by*real*. The default shift value is`closedshell=0.4`.**Note**: Normally this will disable the automatic shift of energies of virtual orbitals! To override this, you should append an exclamation mark to the 'automatic' switch, i.e. specify '`automatic!`*real*'. `individual`-

Set shifts for special occupied MOs. To use this option, start the line with the symmetry label and the list of MOs within this symmetry and append the desired shift in brackets as in the following example:a1 1,2,4-6 (-.34) b1 8 (+.3)

`$scftol`*real*

Integral evaluation threshold. Integrals smaller than*real*will not be evaluated. Note that this threshold may affect accuracy and the convergence properties if it is chosen too large. If`$scftol`is absent, a default value will be taken obtained from`$scfconv`by*real*= (#bf = number of basisfunctions).`$scratch files`

The scratch files allocated by`dscf`can be placed anywhere in your file systems instead of the working directory by referencing their pathnames in this data group. All possible scratch files are listed in the following example:

$scratch files dscf dens path1/file1 dscf fock path2/file2 dscf dfock path3/file3 dscf ddens path4/file4 dscf statistics path7/file7 dscf errvec path8/file8 dscf oldfock path9/file9 dscf oneint path10/file10

The first column specifies the program type (`dscf`

stands for SCF energy calculations, i.e. the`dscf`program), the second column the scratch file needed by this program and the third column the pathname of the file to be used as scratch file.`$statistics`*options*

The following options are allowed`off`- Do not perform integrals statistics
`dscf`- Perform integrals statistics for
`dscf` `kora`- see KORA
`mpgrad`- see
`mpgrad` `polly`- see POLLY
`dscf parallel`- see PARALLEL PROCESSING

`kora, dscf parallel, grad, mpgrad, polly`

will be described in the related chapters.

If`$statistics dscf`

has been given integral prescreening will be performed (which is an*n*^{4}-step and may therefore be time-consuming) and a table of the number of stored integrals as a function of the two parameters`$thize`

and`$thime`

will be dumped. Afterwards, the filespace needed for the current combination of`$thize`

and`$thime`

will be written to the data group (`$scfintunit`) and`$statistics dscf`

will be replaced by`$statistics off`

.`$thime`*integer*

Integral storage parameter, which is related to the time needed to calculate the integral. The larger*integer*the less integrals will be stored. The default value is*integer*= 5. (see also`$thize`,`$statistics`)`$thize`*real*

Integral storage parameter, that determines, together with`$thime`, the number of integrals stored on disc. Only integrals larger than*real*will be stored. The default value is*real*= 0.100E-04.

```
```

```
```

**Subsections**
- RHF/ROHF
- UHF
- DFT
- RI
- RI-JK
- MARI-
*J*
- LHF

- Two-component SCF (GHF)
- Scalar-relativistic Douglas-Kroll-Hess (DKH) Hamiltonian

** Next:** RHF/ROHF
** Up:** Format of Keywords and
** Previous:** The file ufftopology
** Contents**
** Index**
TURBOMOLE