4.4 The General Options Menu

After you specified all data concerning the molecule you want to examine, you are on your way to the last of the four main menus. Before reaching it, you will perhaps get a message like the following:

DO YOU WANT TO DELETE DATA GROUPS LIKE  
    $energy  
    $grad  
    $hessian  
    $hessian (projected)  
    $last energy change  
    $maximum norm of internal gradient  
    $dipgrad  
    $vibrational normal modes  
    $vibrational spectrum  
    $cartesianforce interspace  
LEFT OVER FROM PREVIOUS CALCULATIONS ? DEFAULT(n)

define has scanned your input file for this session and found some data groups which might have become obsolete. If they are still acceptable depends on the changes you made during your present define session. They are obviously incorrect if you changed the molecule under consideration; but any change in the basis sets or the occupation numbers will make them dangerous, too, because you might not know some day if they really refer to the basis set which is defined in this control file. As a rough guide, delete them whenever you have made changes in one of the first three main menus during your define session.

After that you will reach the last main menu of define which helps you to control the actions of all TURBOMOLE programs. The meanings of the various options are explained in more detail in the description of the individual programs, therefore only a short explanation will be given here.

Now have a look at the menu:

 GENERAL MENU : SELECT YOUR TOPIC  
 scf    : SELECT NON-DEFAULT SCF PARAMETER  
 mp2    : OPTIONS AND DATA GROUPS FOR rimp2 and mpgrad  
 cc     : OPTIONS AND DATA GROUPS FOR ricc2  
 ex     : EXCITED STATE AND RESPONSE OPTIONS  
 prop   : SELECT TOOLS FOR SCF-ORBITAL ANALYSIS  
 drv    : SELECT NON-DEFAULT INPUT PARAMETER FOR EVALUATION  
          OF ANALYTICAL ENERGY DERIVATIVES  
          (GRADIENTS, FORCE CONSTANTS)  
 rex    : SELECT OPTIONS FOR GEOMETRY UPDATES USING RELAX  
 stp    : SELECT NON-DEFAULT STRUCTURE OPTIMIZATION PARAMETER  
 e      : DEFINE EXTERNAL ELECTROSTATIC FIELD  
 dft    : DFT Parameters  
 ri     : RI Parameters  
 rijk   : RI-JK-HF Parameters  
 senex  : seminumeric exchange parameters  
 hybno  : hybrid Noga/Diag parameters  
 dsp    : DFT dispersion correction  
 trunc  : USE TRUNCATED AUXBASIS DURING ITERATIONS  
 marij  : MULTIPOLE ACCELERATED RI-J  
 dis    : DISPLAY MOLECULAR GEOMETRY  
 list   : LIST OF CONTROL FILE  
 &      : GO BACK TO OCCUPATION/ORBITAL ASSIGNMENT MENU  
 * or q : END OF DEFINE SESSION

This menu serves very different purposes. The next subsection deals with commands required to activate and/or specify specific methods of calculation. The subsequent subsection describes commands used to select non-default options. Standard SCF calculations do not require special action, just leave the menu. The final subsection describes the settings for property calculations.

4.4.1 Important commands

DFT calculations

Command dft leads you to the menu:

STATUS OF DFT_OPTIONS:  
 DFT is NOT used  
   functional b-p  
     gridsize m3  
 
 ENTER DFT-OPTION TO BE MODIFIED  
 
 func: TO CHANGE TYPE OF FUNCTIONAL  
 grid: TO CHANGE GRIDSIZE  
  on:   TO SWITCH ON  DFT  
 Just <ENTER>, q or ’*’ terminate this menu.

To activate DFT input on and then specify the grid for the quadrature of exchange-correlation terms. TURBOMOLE offers grids 1 (coarse) to 7 (finest), and the multiple grids m3 to m5 [4]. The latter employ a coarser grid during SCF iterations, and grid 3 to grid 5 in the final SCF iteration and the gradient evaluation. Default is grid m3, for clusters with more than 50 atoms use m4.

The functionals supported are obtained with the command func:

SURVEY OF AVAILABLE EXCHANGE-CORRELATION ENERGY FUNCTIONALS  
 
FUNCTIONAL      | TYPE | EXCHANGE       | CORRELATION    | REFERENCES  
---------------------------------------------------------------------  
slater-dirac-   | LDA  | S              |                | 1,2  
exchange        |      |                |                |  
s-vwn           | LDA  | S              | VWN(V)         | 1-3  
vwn             | LDA  |                | VWN(V)         | 3  
s-vwn_Gaussian  | LDA  | S              | VWN(III)       | 1-3  
pwlda           | LDA  | S              | PW             | 1,2,4  
becke-exchange  | GGA  | S+B88          |                | 1,2,5  
b-lyp           | GGA  | S+B88          | LYP            | 1,2,6  
b-vwn           | GGA  | S+B88          | VWN(V)         | 1-3,5  
lyp             | GGA  |                | LYP            | 6  
b-p             | GGA  | S+B88          | VWN(V)+P86     | 1-3,5,7  
pbe             | GGA  | S+PBE(X)       | PW+PBE(C)      | 1,2,4,8  
tpss            | MGGA | S+TPSS(X)      | PW+TPSS(C)     | 1,2,4,14  
bh-lyp          | HYB  | 0.5(S+B88)     | LYP            | 1,2,5,6,9  
                |      | +0.5HF         |                |  
b3-lyp          | HYB  | 0.8S+0.72B88   | 0.19VWN(V)     | 1-3,5,6,10  
                |      | +0.2HF         | +0.81LYP       |  
b3-lyp_Gaussian | HYB  | 0.8S+0.72B88   | 0.19VWN(III)   | 1-3,5,6,10  
                |      | +0.2HF         | +0.81LYP       |  
pbe0            | HYB  | 0.75(S+PBE(X)) | PW+PBE(C)      | 1,2,4,8,11  
                |      | +0.25HF        |                |  
tpssh           | HYB  | 0.9(S+TPSS(X)) | PW+TPSS(C)     | 1,2,4,14,15  
                |      | +0.1HF         |                |  
lhf             | EXX  | EXX            |                | 12,13  
b97-d           | GGA  | B97 refit      | B97 refit      | 16  
b2-plyp         | DHYB |0.47(SB88)+0.53HF|0.73LYP+0.27PT2| 17  


Default is b-p, i.e. B-P86, which is probably best for the whole of Chemistry [27]. For main group compounds we recommend b3-lyp; note that GAUSSIAN uses partly different implementations [27].

The programs dscf and grad are used to carry out conventional DFT treatments, i.e. J and K are evaluated without approximations.

RI-J calculations

For non-hybrid functionals we strongly recommend the RI-J procedure, which speeds up calculations by a factor 10 at least (as compared to conventional treatments) without sacrificing accuracy. Command ri gives:

STATUS OF RI-OPTIONS:  
    RI IS NOT USED  
    Memory for RI:           200 MB  
    Filename for auxbasis: auxbasis  
 
 ENTER RI-OPTION TO BE MODIFIED  
      m: CHANGE MEMORY FOR RI  
      f: CHANGE FILENAME  
   jbas: ASSIGN AUXILIARY RI-J BASIS SETS  
     on: TO SWITCH ON  RI  
 Use <ENTER>, q, end, or * to leave this menu

Activate RI-J with on, and choose with m the memory you can dedicate to store three-center integrals (Keyword: $ricore), default is 200MB. The more memory, the faster the calculation.

A rough guide: put $ricore to about 23 of the memory of the computer. Use OS specific commands (top on most UNIX systems), during an ridft run to find the actual memory usage and then adjust $ricore, the keyword in control specifying memory.

If the option jbas is selected, define enters a submenu which allows the assignment of auxiliary basis sets (for an explanation of the menu items see Section 4.2). Where available, the program will select by default the auxiliary basis sets optimized for the orbital basis used. Please note that treatment of systems with diffuse wavefunctions may also require an extension of the auxiliary basis. For this cases enlarge the sets of s- and p-functions with diffuse functions.

The RI-J option is only supported by programs ridft and rdgrad, if you use jobex to optimize molecular geometry, put: nohup jobex -ri ...

MARI-J option

RI-J calculations can be done even more efficiently with the Multipole Accelerated RI-J (MARI-J) option, especially for larger molecules where almost linear scaling is achieved [28].

Parameters:  
 1) precision parameter:               1.00E-06  
 2) maximum multipole l-moment:              10  
 3) maximum number of bins:                   8  
 4) minimum separation of bins:            0.00  
 5) maximum allowed extension:            20.00  
 6) threshold for multipole neglect:   1.00E-18  
 
Enter the number to change a value or <return> to accept all.

Just rely on the defaults.

Multiple auxiliary basis sets

With the command trunc you can switch on this option. Effect: a reduced auxiliary (or fitting) basis to represent the electron density is employed during SCF iterations, the final SCF iteration and the gradient are computed with the full auxiliary basis.

 truncated RI ALREADY SWITCHED ON  
 DO YOU WANT TO SWITCH OFF truncation ? (default=no)

Note: trunc is presently not compatible with marij!

RI in SCF calculations

Considerable savings in CPU times are achieved with the RI technique for both Coulomb J and exchange K terms in SCF calculations, the RI-JK method [29], provided large basis sets are employed, e.g. TZVPP, cc-pVTZ, or cc-pVQZ. With rijk you get:

STATUS OF RI-OPTIONS:  
    RI IS NOT USED  
    Memory for RI:           200 MB  
    Filename for auxbasis: auxbasis  
 
 ENTER RI-OPTION TO BE MODIFIED  
      m: CHANGE MEMORY FOR RI  
      f: CHANGE FILENAME  
  jkbas: ASSIGN AUXILIARY RI-JK BASIS SETS  
     on: TO SWITCH ON  RI  
 Use <ENTER>, q, end, or * to leave this menu

For an explanation of the menu items see Section 4.4.1. RI-JK calculations can be carried out with the program ridft.

Optimization to minima and transition structures using STATPT

Structure optimizations can be carried out by the program statpt. For minimizations no additional keywords are required. The default values are assumed, which work in most of the cases. Structure optimization is performed in internal coordinates if they have been set. Otherwise, Cartesian coordinates are used. One can switch the optimization in internal coordinates on or off, respectively in internal redundant or cartesian coordinates. For transition structure optimizations the index of transition vector has to be set to an integer value > 0 (0 means structure minimization). The value of the index specifies transition vector to follow during the saddle point search. Note, that Hessian eigenpairs are stored in ascending order of the eigenvalues, i.e. the eigenpair with the smallest eigenvector has the index 1.

The command stp gives:

 ------------------------------------------------------------------------  
 CONVERGENCE CRITERIA:  
 
 thre  1.000000E-06     thre : threshold for ENERGY CHANGE  
 thrd  1.000000E-03     thrd : threshold for MAX. DISPL. ELEMENT  
 thrg  1.000000E-03     thrg : threshold for MAX. GRAD. ELEMENT  
 rmsd  5.000000E-04     rmsd : threshold for RMS OF DISPL.  
 rmsg  5.000000E-04     rmsg : threshold for RMS OF GRAD.  
 
 defl : set default values.  
 
 ------------------------------------------------------------------------  
 
 OPTIMIZATION refers to  
 
 int   off         int: INTERNAL coordinates  
 rdn   off         rdn: REDUNDANT INTERNAL coordinates  
 crt   on          crt: CARTESIAN coordinates  
 NOTE : options int and crt exclude each other  
 
 ENTER STATPT-OPTIONS TO BE MODIFIED  
 
 itvc    0              itvc : change INDEX OF TRANSITION VECTOR  
 updte   bfgs           updte: change method of HESSIAN UPDATE  
 hsfrq   0              hsfrq: frequency of HESSIAN CALCULATION  
 kptm    0              kptm : FREEZING transition vector INDEX  
 hdiag 5.000000E-01     hdiag: change DIAGONAL HESSIAN ELEMENTS  
 rmax  3.000000E-01     rmax : change MAX. TRUST RADIUS  
 rmin  1.000000E-04     rmin : change MIN. TRUST RADIUS  
 trad  3.000000E-01     trad : change TRUST RADIUS  
 ------------------------------------------------------------------------  
 Just <ENTER>, q or ’*’ terminate this menu.  

Excited states, frequency-dependent properties, and stability analysis

Excited state calculations with RPA or CIS (based on HF-SCF) and TDDFT procedures as well as stability analyses (SCF or DFT) are carried out by the program escf.

You will need a well converged HF-SCF or DFT calculation that were converged to at least $scfconv=7, see Section 4.4.2.

Details of calculations are specified with the command ex:

MAIN MENU FOR RESPONSE CALCULATIONS  
 
OPTION | STATUS | DESCRIPTION  
-------------------------------------------------------------------  
rpas   | off    | RPA SINGLET EXCITATIONS (TDHF OR TDDFT)  
ciss   | off    | TDA SINGLET EXCITATIONS (CI SINGLES)  
rpat   | off    | RPA TRIPLET EXCITATIONS (TDHF OR TDDFT)  
cist   | off    | TDA TRIPLET EXCITATIONS (CI SINGLES)  
polly  | off    | STATIC POLARIZABILITY  
dynpol | off    | DYNAMIC POLARIZABILITY  
single | off    | SINGLET STABILITY ANALYSIS  
triple | off    | TRIPLET STABILITY ANALYSIS  
nonrel | off    | NON-REAL STABILITY ANALYSIS  
 
ENTER <OPTION> TO SWITCH ON/OFF OPTION, * OR q TO QUIT

If you have selected an option, e.g. rpas, and quit this menu, you will get another menu:

SELECT IRREP AND NUMBER OF STATES  
ENTER ? FOR HELP, * OR Q TO QUIT, & TO GO BACK

This should be self-evident.

MP2 and RI-MP2

We recommend to use MP2 together with the RI technique: program rimp2 or  ricc2. This is more efficient and supports the frozen core option in the gradient calculation.

The entry mp2 leads to a submenu which allows to set some keywords for MP2 and RI-MP2 calculations, e.g. defining frozen orbitals, maximum memory usage, or assign auxiliary basis sets for RI-MP2 calculations, etc. If you want to use ricc2, you have to use the entry cc2 and the submenu ricc2 in order to assign MP2 as wavefunction model. It covers all keywords required for rimp2 calculations, Mandatory for rimp2 runs is the specification of the auxiliary basis set using the menu entry cbas. (Alternatively, the rimp2prep tool can be used to set the keywords needed for rimp2 calculations.)

Conventional MP2 calculations with mpgrad require a number of additional settings for which it is recommended to invoke the interactive tool mp2prep. For geometry optimizations with jobex use nohup jobex -level mp2 -ri ...

CC2 calculations

The entry cc2 leads to a submenu which allows to set a number of keywords essential for calculations with the program ricc2. In particular it allows the assignment of auxiliary basis sets (mandatory for ricc2!), the specification of frozen orbitals, and the definition of a scratch directory and of the maximum core memory usage.

2nd analytical derivatives

The program aoforce computes force constants and IR and Raman Spectra on SCF and DFT level. Analytical second derivative calculations can directly be started from converged SCF or DFT calculations. Note, that the basis is restricted to d-functions, and ROHF as well as broken occupation numbers are not allowed. For better efficiency, in case of larger systems, use the keyword $maxcor as described in Chapter 13 to reduce computational cost. RI will be used if the RI option for DFT has been specified.

4.4.2 Special adjustments

Adjustments described by the following menus are often better done directly in the control file; have a look at the keywords in Chapter 20. For common calculations just start with the defaults, and change keywords directly in control if you encounter problems with your calculation.

SCF options
ENTER SCF-OPTION TO BE MODIFIED  
 
conv : ACCURACY OF SCF-ENERGY           $scfconv  
thi  : INTEGRAL STORAGE CRITERIA        $thize  $thime  
ints : INTEGRAL STORAGE ALLOCATION      $scfintunit  
iter : MAXIMUM NUMBER OF ITERATIONS     $scfiterlimit  
diis : DIIS CONVERGENCE ACCELERATION    $scfdiis  
damp : OPTIONS FOR DAMPING              $scfdamp  
shift: SHIFTING OF ORBITALS             $scforbitalshift  
order: ORDERING OF ORBITALS             $scforbitalorder  
fermi: THERMAL SMEARING OF OCC. NUMBERS $fermi

By the command $fermi you can switch on smearing of occupation numbers, and thus automatically optimize occupations and spin.

Menu drv

The most important of the derivative menus is the first one which tells the programs which derivatives to calculate. This is only necessary for special purposes and you should better not change default options.

------------------------------------------------------------------------  
 derivative data groups ’$drvopt, $drvtol’  
------------------------------------------------------------------------  
 option | status  | description :  
------------------------------------------------------------------------  
 crt    |    T    | CARTESIAN 1st derivatives  
 sec    |    T    | CARTESIAN 2nd derivatives  
 bas    |    F    | energy derivatives with respect to  
        |         |  BASIS SET exponents/scaling factors/  
        |         |  contraction coefficients  
 glb    |    F    | energy derivative with respect to  
        |         |  a GLOBAL scaling factor  
 dip    |    T    | cartesian 1st derivatives of DIPOLE MOMENT  
 pol    |    T    | nuclear contribution to POLARIZABILITY  
 fa     |    F    | SPECTROSCOPIC ANALYSIS only  
 tol     0.100D-06  derivative integral cutoff  
------------------------------------------------------------------------  
 use <opt> for enabling, -<opt> for disabling of logical switches  
 <&> will bring you back to GENERAL MENU without more changes  
 <RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU

The handling of these options is very simple. With the exception of tol, all are logical switches which are either true (or on, active) or false (or off, inactive). You can switch between the two states if you enter, for example, crt (to switch calculation of Cartesian first derivatives on) or -crt (to switch it off). The options crt, sec and bas should provide no problems. glb refers to a global scaling factor for all basis set exponents. Imagine that you would like to replace your basis set, which contains basis functions

                                  [           ]
χμ = (x - x0)l(y - y0)m (z - z0)nexp - ημ(r - r0)2

by another basis set which contains basis functions

χ  = (x - x )l(y - y )m(z - z)n exp[- αη (r - r)2]
  μ        0       0        0          μ     0

where α is the same for all primitive basis functions χμ. With command glb you are able to calculate analytical derivatives of the total energy with respect to α and can thus easily determine the optimum α.

dip enables you to calculate the first derivatives of the electric dipole moment with respect to nuclear displacements which gives you infrared intensities. pol allows you to calculate the contribution of the nuclear rearrangement on the electric polarizability. fa finally performs only a frequency analysis which means that aoforce will read the force constant matrix ($hessian or $hessian (projected)), diagonalize it and give you the frequencies and normal modes. tol is not a logical switch as the other options in this menu, but a cutoff threshold for the derivative integrals, i.e. integrals below this threshold will be neglected in the derivative calculations.

Entering * will bring you to the second derivative submenu.

Debug Options for the Derivative Programs

The following menu deals only with some debug options for grad. Use them with caution, each of them can produce lots of useless output:

------------------------------------------------------------------------  
 derivative debug options ’$drvdebug’  
------------------------------------------------------------------------  
 option  |status| description :  
------------------------------------------------------------------------  
 disp1e  |   F   | display 1e contributions to desired derivatives  
 only1e  |   F   | calculate 1e contributions to desired derivatives only  
 debug1e |   F   | display 1e shell contributions to desired derivatives  
         |       |  (WARNING : this produces large outputs!)  
 debug2e |   F   | display 2e shell contributions to desired derivatives  
         |       |  (WARNING : this produces VERY large  outputs!)  
 debugvib|   F   | debug switch for vibrational analysis (force only)  
 notrans |   F   | disable transfer relations (gradient only!)  
 novirial|   F   | disable virial scaling invariance in basis set  
         |       |  optimizations (gradient only)  
------------------------------------------------------------------------  
 use <opt> for enabling, -<opt> for disabling option <opt>  
 <&> will bring you back to GENERAL MENU without more changes  
 <RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU


As there is no need to use these options normally and the menu text is self-explaining, no further description will be given. Note that all options are logical switches and may be enabled and disabled the same way as shown for the last menu. Entering * will bring you to the last derivative submenu.

4.4.3 Relax Options

Program relax has a huge variety of options to control its actions which in program define are grouped together in eight consecutive menus. These are only briefly described in the following sections; for a more detailed discussion of the underlying algorithms refer to the documentation of program relax (see Section 5.3). Only experts should try to change default settings.

Optimization Methods

The first of the relax subgenus deals with the type of optimization to be performed:

------------------------------------------------------------------------  
 optimization options for RELAX  
------------------------------------------------------------------------  
 option | status | description : optimization refers to  
------------------------------------------------------------------------  
 int    |    F   | INTERNAL coordinates  
 crt    |    F   | CARTESIAN coordinates  
 bas    |    F   | BASIS SET exponents/scale factors  
 glb    |    F   | GLOBAL scaling factor  
------------------------------------------------------------------------  
 use <opt> for enabling, -<opt> for disabling option <opt>  
 <RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU


You can choose between a geometry optimization in the space of internal coordinates (in this case you will need definitions of internal coordinates, of course) or in the space of Cartesian coordinates (these possibilities are mutually exclusive, of course). Furthermore optimizations of basis set parameters (exponents, contraction coefficients and scaling factors) or of a global scaling factor is possible (these options are also exclusive, but can be performed simultaneous to a geometry optimization). For the geometry optimization you should normally use internal coordinates as they provide better convergence characteristics in most cases.

Coordinate Updates

The next submenu deals with the way relax updates the old coordinates. You may choose a maximum change for the coordinates or you can allow coordinate updates by means of extrapolation:

------------------------------------------------------------------------  
 coordinate update options for RELAX  
------------------------------------------------------------------------  
 dqmax <real> : coordinates are allowed to change by at most  
                <real> (DEFAULT : 0.3000    ) a.u.  
 polish       : perform an interpolation or extrapolation of  
                coordinates (DEFAULT :y)  
 -polish      : disable inter/extrapolation  
------------------------------------------------------------------------  
 <RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU


These options result in better convergence of your optimization in most cases.

Interconversion Between Internal and Cartesian Coordinates

The interconversion between internal and Cartesian coordinates is not possible directly (in this direction). Instead it is performed iteratively. The following options control this conversion:

--------------------------------------------------------------------  
interconversion options for RELAX  
--------------------------------------------------------------------  
option    | description  
--------------------------------------------------------------------  
on        | switch on interconversion (DEFAULT: off)  
qconv <r> | set convergence threshold for interconversion  
          | of coordinates to <r>. DEFAULT : <r> =  .1000E-09  
iter <i>  | allow at most <i> iterations for interconversion  
          | of coordinates. DEFAULT : <i> =   25  
crtint    | transform cartesian into internal coordinates (DEFAULT=n)  
intcrt    | transform internal into cartesian coordinates (DEFAULT=n)  
grdint    | transform cartesian into internal gradients (DEFAULT=n)  
hssint    | transform cartesian into internal hessian (DEFAULT=n)  
--------------------------------------------------------------------  
use -<opt> for disabling any interconversion option  
<RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU


The options qconv and iter are used in each normal relax run to determine the characteristics of the back-transformation of coordinates into the internal space. With the other options and interconversion switched on, you can force relax to perform only the specified coordinate transformation and write the transformed coordinates to file control. To achieve this, enter on to switch to the transformation-only mode, and one of the last four options, e.g. crtint, to specify the desired transformation.

Updating the Hessian

relax provides a variety of methods to generate an updated Hessian every cycle. This includes the well known methods such as BFGS, DFP, or MS update methods as well as some less common procedures:

--------------------------------------------------------------  
OPTIONS FOR UPDATING THE HESSIAN  
--------------------------------------------------------------  
 option  | status | description  
--------------------------------------------------------------  
none     |    F   | NO UPDATE (STEEPEST DESCENT)  
bfgs     |    F   | BROYDEN-FLETCHER-GOLDFARB-SHANNO UPDATE  
dfp      |    F   | DAVIDON-FLETCHER-POWELL UPDATE  
bfgs-dfp |    F   | COMBINED (BFGS+DFP) UPDATE  
ms       |    F   | MURTAGH-SARGENT UPDATE  
schlegel |    F   | SCHLEGEL UPDATE  
diagup   |    F   | DIAGONAL UPDATE (AHLRICHS/EHRIG)  
multidim |    F   | RANK > 2 BFGS-TYPE UPDATE  
ahlrichs |    T   | MACRO : AHLRICHS UPDATE (DEFAULT)  
--------------------------------------------------------------  
USE <opt> FOR ENABLING OPTION <opt> AND THUS DISABLING  
ALL OTHER OPTIONS.  
<RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU


We recommend to use the default method ahlrichs which provides excellent convergency in most cases.

General Boundary Conditions for Update

The force constant matrix will only be updated if least mingeo cycles exist. The maximum number of cycles used for the update is specified by the parameter maxgeo. Normally the default values provided by define need not be changed.

DEFINE BOUNDARY CONDITIONS FOR UPDATE  
--------------------------------------------------------------  
mingeo <i> | START UPDATE IF THERE ARE AT LEAST <i> CYCLES  
           | DEFAULT : min   3  
maxgeo <i> | USE LAST <i> CYCLES FOR UPDATE, DEFAULT : max   4  
--------------------------------------------------------------  
<RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU

Special Boundary Conditions for Ahlrichs and Pulay Updates

For the default update method ahlrichs some additional control parameters are available which can be defined in this menu:

DEFINE BOUNDARY CONDITIONS FOR AHLRICHS OR PULAY UPDATE  
--------------------------------------------------------------  
option    | description  
--------------------------------------------------------------  
modus <i> | DEFINE MODUS FOR GDIIS PROCEDURE : MINIMIZE  
          |  <dq|dq> IF  <i> = 0  
          |  <g|dq>  IF  <i> = 1  
          |  <g|g>   IF  <i> = 2  
          |  <dE>    IF  <i> = 3  
          | DEFAULT : <i> = 1  
fail <r>  | IGNORE GDIIS IF  <g|dq> /| <g|dq> | IS  
          | LARGER THAN -<r>. DEFAULT : <r> = 0.1  
--------------------------------------------------------------  
<RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU

For detailed description consult Section 5.3.

--------------------------------------------------------------  
OPTIONS FOR MANIPULATING THE HESSIAN  
--------------------------------------------------------------  
 option      | description  
--------------------------------------------------------------  
diagonal     | RESTRICT UPDATE TO DIAGONAL-ELEMENTS IF  
             | METHOD IS BFGS,DFP OR MS. DEFAULT=n  
offreset     | DISCARD OFF-DIAGONAL ELEMENTS. DEFAULT=n  
offdamp <r>  | DAMP OFF-DIAGONAL ELEMENTS BY 1/(1+<r>) DEFAULT= 1.000  
damp <real>  | DAMP UPDATE BY 1/(1+<real>), DEFAULT= .0000E+00  
scale <real> | SCALE INPUT HESSIAN BY <real>, DEFAULT= 1.000  
allow <real> | SCALE INPUT HESSIAN BY <real>/|DE| IF |DE|,  
             | THE OBSERVED ABSOLUTE CHANGE IN ENERGY, IS  
             | OBEYING THE CONDITION |DE| > <real> > 0.  
             | DEFAULT : NO SCALING  
min <real>   | DO NOT ALLOW EIGENVALUES OF HESSIAN TO DROP  
             | BELOW <real>. DEFAULT= .1000E-02  
reset <real> | USE <real> AS A RESET VALUE FOR TOO SMALL  
             | EIGENVALUES (CP. min). DEFAULT= .1000E-02  
max <real>   | DO NOT ALLOW EIGENVALUES OF HESSIAN TO BECOME  
             | LARGER THAN <real>. DEFAULT= 1000.  
--------------------------------------------------------------  
WITH THE EXCEPTION OF min,reset AND max, ALL OPTIONS MAY BE  
DISABLED BY ENTERING -<opt>  
<RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU

Initialization of the Hessian

Finally there are some options to control the choice of the initial Hessian during your geometry optimization:

--------------------------------------------------------------  
FORCE CONSTANTS INITIALIZATION OPTIONS FOR RELAX  
--------------------------------------------------------------  
OPTION    | DESCRIPTION  
--------------------------------------------------------------  
off       | switch off initialization (DEFAULT: on)  
cart      | use analytical cartesian hessian provided by a  
          | 2nd derivatives calculation. DEFAULT(n)  
diag      | use diagonal matrix with diagonal elements set  
          | individually within data groups $intdef or  
          | $basis or $global. DEFAULT(n)  
unit <r>  | use multiple of the unit matrix ( H = <r>*E ).  
          | DEFAULT(n) - DEFAULT <r> =  1.000  
--------------------------------------------------------------  
NOTE THAT THESE OPTIONS ARE MUTUALLY EXCLUSIVE  
<RETURN> OR * OR q(uit) WILL TERMINATE THIS MENU


Option off will be used if you have already a good Hessian from a previous calculation which may be used. cart describes an even better state where you have a Hessian from a calculation of the second derivatives available (aoforce). The other two options describe real procedures for initialization of the Hessian. Default values: stretches (0.5), angles (0.2).

4.4.4 Definition of External Electrostatic Fields

This submenu allows you to calculate first and second numerical derivatives of the energy with respect to an external electric field. The first three options should be clear; 1st and 2nd are logical switches which are turned on and off the usual way (1st or -1st) and delta is the increment for the numerical differentiation, that is, the finite value of the external field, which replaces the (ideally) differential field:

--------------------------------------------------------------------  
electrostatic field definition menu  
--------------------------------------------------------------------  
option       | status | description  
--------------------------------------------------------------------  
1st          |    F   | numerical 1st derivative dE/dField  
2nd          |    F   | numerical 2nd derivative d2E/dField2  
delta <real> |        | increment for numerical differentiation  
             |        | DEFAULT =    .5000E-02  
geofield     |    F   | geometry optimization with external field  
man          |    F   | explicit definition of electrostatic field(s)  
--------------------------------------------------------------------


geofield gives the possibility to perform a whole geometry optimization under the influence of a finite external field and thus to obtain the (distorted) minimum geometry in this field. To do this, an external electrostatic field must be defined explicitly which can be done using command man. Note that geofield must also be switched on if any properties are to be evaluated in the presence of an electric field. The most prominent example is the calculation of hyperpolarizabilies.

Take Care, due to some inconsistencies in define it is always necessary to switch on the field calculations manually. Therefore edit the control file after having finished your define session and enter on after the entries of fields and geofield.

4.4.5 Properties

The program moloch used for this purpose is currently being revamped, and will then be much simpler to use. The subsequent description for an older version may not work in all cases—sorry for that.

If you enter prop in the general menu, define first will check whether the data group $properties does already exist in your control file or in a file referenced therein. If this is not the case you will be asked to specify the file on which $properties shall be written:

data group $properties has not yet been specified  
FOR INITIALIZING <moloch> KEYWORDS ENTER  
  [return] : WRITE TO CONTROL FILE control (DEFAULT),   OR  
  filename : WRITE TO ANOTHER FILE


Afterwards you will get the following submenu which allows you to control all possible actions of program moloch:
switch on one or more of the following options <i>  
<i> = 1,..., 9  
for switching off option <i>, specify -<i>  
( 1) trace                                     off  
( 2) moments                                   off  
( 3) potential                                 off  
( 4) cowan-griffin                             off  
( 5) localization                              off  
( 6) population analyses                       off  
( 7) plot                                      off  
( 8) firstorder                                off  
selecting an already active option indicates that  
suboptions shall be modified  
* or q(uit) = quit | for help, type help <integer>


All options in this menu are selected by entering their number as indicated in the first column. For example, to switch on option trace enter 1. The flag off will then change to active. To switch off an option enter its negative number, e.g. -1 for trace. Most of the options require additional input and will therefore lead you to further submenus. These are briefly described below.

Option trace

trace will calculate the trace of density times overlap matrix:

N =  tr{DS }

If the orbitals are orthonormal, N should yield the total number of electrons in your molecule. If this is not true, your MO-vector will most probably be erroneous. For example, the vector might belong to another geometry or basis set. As this is a very sensitive test for errors like these and the calculation requires almost no time, you should always switch on this option.

Option moments

This option leads you to the following submenu:

add/change options for data group $moments  
option            | status | description  
------------------|--------|-------------------------------  
point <x> <y> <z> |    T   | reference point = (x,y,z)  
atom <i>          |    F   | reference point = atom no. <i>  
0th               |    T   | compute 0th moment  
1st               |    F   | compute 1st moment  
2nd               |    F   | compute 2nd moment  
3rd               |    F   | compute 3rd moment  
------------------|--------|-------------------------------  
-<moment>   : skip computation of <moment>  
* or q(uit) : terminate input


This menu serves to specify the electrostatic moments to be calculated (0th=charge, 1st=dipole moment, 2nd=quadrupole moment, 3rd=octuple moment). The reference point is the origin of the coordinate system used in the calculation. The value of any calculated moment will be independent of this reference point, if all lower moments are zero. The default for the reference point is the origin, i.e. the coordinate system used for the calculation of the moments will be the same as the one in which the atomic coordinates are specified. The reference point may be changed by typing point with the three new coordinates appended. Alternatively you may choose the coordinates of one of the atoms as reference point by entering atom and the atom index.

Option potential

This option collects all possible quantities related to the electrostatic field created by the molecular charge distribution. This includes the following suboptions:

list of suboptions :  
pot          - electrostatic potential  
fld          - electrostatic field  
fldgrd       - electrostatic field gradient  
shld         - diamagnetic shielding  
file         - file reference  
*            - quit


The meaning of the four suboptions pot, fld, fldgrd and shld will probably present no problems to you. For each of them, however, you will have to specify at which point(s) this property should be calculated. This is accomplished by one or more data groups $points in file control. After you chose one or more of the above options, you will therefore reach the next submenu which deals with the specification of these data groups:
there are     1 data groups $points  
manipulate data group(s) $points  
a             - add another data group  
m <integer>   - modify <integer>th data group  
m all         - modify all data groups  
d <integer>   - delete <integer>th data group  
d all         - delete all data groups  
off <integer> - switch off <integer>th data group  
off all       - switch off all data groups  
on <integer>  - switch on <integer>th data group  
on all        - switch on all data groups  
s             - scan through data groups  
*             - quit


The first line informs you how many of these data groups already exist in your control file. Each of these data groups may consist of several points at which the properties will be calculated. You may now create new data groups, delete old ones or simply switch on or off individual data groups (without deleting them from control). The number of different data groups $points as well as the number of points in each of them are not limited. However, if you use many points, you should consider specifying them in a separate file. This is most easily done using option file in the potential menu. This option will create a file for your data groups $points and will write a reference of this file to file control.

Option cowan-griffin

This option activates the computation of the first order relativistic correction to the energy as given by the expectation value of the Cowan–Griffin operator.

Option localization

Specifying option localization will switch on a Boys localization of molecular orbitals. define by default chooses a set of MOs to be localized according to a certain threshold for the orbital energy. Information about these are displayed like this:

BOYS localization will be performed with respect to x y z  
number of sweeps =      10000  
subset of molecular orbitals to be localized :  
---> all occupied molecular orbitals  
     with orbital energy above -2.00000     Hartree  
----------------------------------------------------------------  
 shells to be localized  
----------------------------------------------------------------  
a1       4-5                                         #   1-   5  
e        2                                           #   1-   2  
----------------------------------------------------------------  
you are employing default options for localization  
do you want to modify them ? DEFAULT(n)


If you want to change the MO selection or other options for the localization enter y at this point (By default or when typing n you will reach the moloch options menu again). You will then be asked whether to change the MO selection method. If you want this, you will enter a little submenu where you can choose one of three possible selection procedures:
all

selects all occupied orbitals

thr

selects all occupied orbitals with orbital energy larger than a certain threshold

man

enables you to select the MOs manually later in this section

If the selection method thr is specified you then will be asked for the threshold to be applied for the selection. Afterwards you have the possibility to change some other topics concerning the localization:

Option population analyses

When activating this option you first have to specify whether the population analysis (PA) should be performed in the CAO (default) or AO basis. Afterwards define will ask you whether you want to perform a Mulliken population analysis. In this case, the following submenu will be displayed:

add or delete one or more special options for a  
mulliken population analysis  
 option | status | description  
 -------|--------|---------------------------------------  
 spdf   |    F   | compute MO contributions to atomic  
        |        | brutto populations  
 molap  |    F   | compute MO contributions to atomic  
        |        | overlap populations  
 netto  |    F   | compute atomic netto populations  
 irpspd |    F   | compute IRREP contributions to atomic  
        |        | brutto populations  
 irpmol |    F   | compute IRREP contributions to atomic  
        |        | overlap populations  
 mommul |    F   | print electrostatic moments resulting  
        |        | from atomic charges  
 -------|--------|---------------------------------------  
 -<option>   : switch off <option>  
 * or q(uit) : leave this menu


Here you can activate several optional quantities to be computed along with the Mulliken PA. To switch on one or more of these options you must enter the corresponding option keywords, e.g. spdf netto for computation of atomic neto populations and MO contributions to atomic brutto populations. The status flags for these tasks will then change from F (false) to T (true). To switch off any option you simply have to enter the corresponding keyword preceded by a ‘-’, e.g. -netto for disabling calculation of atomic netto populations.

After having left the Mulliken PA section you will be asked whether a population analysis based on occupation numbers (a modified Roby–Davidson PA) should be performed by moloch. When typing y you will see the following submenu, where you can switch on several special options for the PA in the same manner as described above.

add or delete one or more special options for a  
population analysis based on occupation numbers  
 option  | status | description  
 --------|--------|----------------------------------------  
 momao   |    F   | compute MO contributions to modified  
         |        | atomic orbital (MAO) occupation numbers  
 maodump |    F   | dump all MAOs onto standard output  
 maofile |    F   | write MAOs onto a separate file  
 select  |    F   | write only those MAOs which have been  
         |        | employed in the population analysis  
 all     |    F   | write all MAOs  
 --------|--------|----------------------------------------  
 note that the options select and all are complementary  
 -<option>   : switch off <option>  
 * or q(uit) : leave this menu


Afterwards you have the possibility to change the criterion to be applied for the selection of modified atomic orbitals (MAOs) within the following little submenu:
global criterion for selection of Modified Atomic Orbitals (MAOs) :  
-------------------------------------------------------------------  
 MAOs are employed if ’atomic’ density eigenvalues  
 exceed a threshold of  .1000  
-------------------------------------------------------------------  
 specify the appropriate option if you want to use another  
 global criterion for selecting MAOs  
 option  | status | description  
 --------|--------|---------------------------------------  
 eig <r> |    T   | select by eigenvalues of the  
         |        | ’atomic’ density matrices  
 occ <r> |    F   | select by occupation numbers  
 --------|--------|---------------------------------------  
 <r> is the selection threshold (DEFAULT= .1000    )  
 * or q(uit) : leave this menu


The criterion applied by default is the so-called atomic density eigenvalue with a threshold of 0.1. You can switch the criterion to occupation numbers by entering occ. If you also want to change the threshold, you just have to append its new value to the selection keyword, e.g. occ .2. Finally you can select or disable various options in connection with the computation of shared electron numbers (SEN) within the following menu:
actual settings for data group $shared electron numbers  
 2-center shared electron numbers will be computed;  
 values are printed if absolute value exceeds    .0100  
 3-center shared electron numbers will be computed;  
 values are printed if absolute value exceeds    .0100  
 4-center shared electron numbers will be computed;  
 values are printed if absolute value exceeds    .0100  
add or delete one or more options for the  
computation of Shared Electron Numbers (SEN)  
 option  | status | description  
 --------|--------|----------------------------------------  
 2c <r>  |    T   | compute 2-center SEN and print if  
         |        | |SEN| > <r> (DEFAULT =  .1000E-01)  
 3c <r>  |    T   | compute 3-center SEN and print if  
         |        | |SEN| > <r> (DEFAULT =  .1000E-01)  
 4c <r>  |    T   | compute 4-center SEN and print if  
         |        | |SEN| > <r> (DEFAULT =  .1000E-01)  
 --------|--------|----------------------------------------  
 nosym   |    F   | switch off use of symmetry  
 orbs    |    F   | compute orbital contributions to SEN  
 irreps  |    F   | compute irrep contributions to SEN  
 --------|--------|----------------------------------------  
 -<option>   : switch off <option>  
 * or q(uit) : leave this menu


The procedure for changing the options is the same as described above. By default calculation of 2-, 3- and 4-center SENs will be enabled with thresholds of 0.01 each.

Option plot

This option allows you to prepare the data needed for contour plots of orbital amplitudes or total electron densities. We do not recommend to prepare plotting data this way; an easier method—with an easier syntax—is to generate these data directly by the programs, where densities (also MP2 or excited ones) and Molecular orbitals are calculated. This is described in Chapter 16. If you nevertheless want to prepare the input for plotting data as needed by moloch using define, on activating plot you get the following menu:

there are     1 data groups $grid  
manipulate data group(s) $grid  
 a             - add another data group  
 m <integer>   - modify <integer>th data group  
 m all         - modify all data groups  
 d <integer>   - delete <integer>th data group  
 d all         - delete all data groups  
 off <integer> - switch off <integer>th data group  
 off all       - switch off all data groups  
 on <integer>  - switch on <integer>th data group  
 on all        - switch on all data groups  
 s             - scan through data groups  
 *             - quit


The commands in this menu serve for the manipulation of data groups $grid in an analogous way as described for $points in the potential section above. $grid data groups contain the input information necessary to create the plot data by moloch (one data group for each plot). If you want to add a new data group you will enter this submenu:
specify the input orbital / input density :  
mo <label>    - use occupied molecular orbital <label>  
mo density    - use one electron density built from the  
                occupied molecular orbitals  
lmo <i>       - use localized molecular orbital no. <lmo>  
mao <i> <k>   - use modified atomic orbital no. <i>  
                centered on atom no. <k>  
help          - explanation of the syntax for <label>  
*             - quit


Here you may specify the orbital to be plotted. To plot the amplitude of the fifth orbital in irrep a1, e.g., you would enter mo 5a1. Equivalently you can use localized orbitals from a Boys localization procedure or modified atomic orbitals as obtained in a Roby–Davidson–Ahlrichs–Heinzmann population analysis. In the latter cases you will not have to enter an irrep label, as these orbitals are necessarily in C1 symmetry. Instead you will have to enter the index of the orbital to be plotted (and for option mao the index of the atom at which it is situated). In all cases you will additionally have to specify the plane in which the amplitudes or densities will be monitored. To do this, you have to declare two vectors which span that plane and the origin of this new coordinate system relative to the one in which the atomic coordinates are given. Furthermore, you will have to create a grid of points on this plane. The orbital amplitude or electron density will then be calculated for every point in this grid. The grid is created by telling define the range to be included along both vectors spanning the plane (where the unit in each direction is the length of the corresponding basis vector) and the number of points to be calculated in this range. It is advantageous to use a wide grid while you test the ranges or planes which give the best results and then to switch to a finer grid for the final calculation. Finally input (MO vector) and output (plot data) files can be specified.

In case you do not want to add a new data group as described above but to change an existing one, you will be asked which one of the specifications you want to modify.