Differences

This shows you the differences between two versions of the page.

Link to this comparison view

Both sides previous revision Previous revision
Next revision
Previous revision
pes_generators [2020/07/15 15:03]
qianli
pes_generators [2022/02/28 08:35] (current)
rauhutmoschneide [Scaling of individual coordinates]
Line 28: Line 28:
 The following //options// are available: The following //options// are available:
  
 +  * **''BATCH3D''=//n//** After calculating a number of grid points within the iterative interpolation scheme the convergence of the individual surfaces will be checked and, if provided by the keyword ''DUMP'', dumped to disk. This leads typically to 3-5 iterations and thus the same number of restart points within the calculation of the 1D, 2D, ... surfaces. As the number of 3D and 4D terms can be very large this is not sufficient in these cases. Therefore, the lists of 3D and 4D terms is cut into batches which will be processed subsequently. ''BATCH3D'' and ''BATCH4D'' control the number of 3D and 4D surfaces within each batch. By default ''BATCH3D'' is set to 30 times the number of processors and ''BATCH4D'' to 10 times the number of processors. Accordingly the number of restart points is increased. Smaller values for ''BATCH3D'' and ''BATCH4D'', e.g. ''BATCH3D=20'', increase the number of restart points on cost of the efficiency of the parallelization. Note, this keyword is only relevant for ''SURF'' calculations, but not for ''XSURF'' runs.
 +  * **''DELLOG''=//n//** For large molecules or in the case of modelling the 3D and 4D terms, the .log-file may become huge. First of all the .log-file can be directed to scratch within the electronic structure program, i.e. ''logfile'', ''scratch''. The option ''DELLOG=1'' always truncates the .log-file in a way that it contains only the very last energy calculation. Default: ''DELLOG=0''.
 +  * **''EXT12D''=//value//** Outer regions of the potential energy surfaces may be determined by extrapolation rather than interpolation schemes. By default extrapolation is switched off, i.e. ''Ext12D=1.0'' and ''Ext34D=1.0''. However, an extrapolation of 10% in case of the 1D and 2D contributions to the potential (''Ext12D=0.9'') and of 20% in case of the 3D and 4D terms (''Ext34D=0.8'') may be useful as it usually stabilizes the fitting procedure.
 +  * **''FIT1D''=//n//** The maximum order of the polynomials used for fitting within the iterative interpolation scheme can be controlled by the keywords ''%%FIT1D, FIT2D, FIT3D, FIT4D%%''. The default is given by 8. However in certain cases higher values may be necessary, but require an appropriate number of coarse grid points, which can be controlled by ''MIN1D'' etc.
 +  * **''INFO''=//n//** ''INFO=1'' provides a list of the values of all relevant program parameters (options). Default: ''INFO=0''.
 +  * **''MAX1D''=//n//** The maximum number of coarse grid points can be controlled by the keywords ''%%MAX1D, MAX2D, MAX3D, MAX4D%%''. These 4 keywords determine the maximum number of //ab initio// calculations in one dimension for each 1D, 2D, 3D and 4D surface. The defaults are currently ''MAX1D=24'', ''MAX2D=16'', ''MAX3D=10'', ''MAX4D=8''. Presently, values larger than 24 are not supported.
 +  * **''MIN1D''=//n//** The minimum number of coarse grid points can be controlled by the keywords ''%%MIN1D, MIN2D, MIN3D, MIN4D%%''. These 4 keywords determine the minimum number of //ab initio// calculations in one dimension for each 1D, 2D, 3D and 4D surface. The defaults are currently ''%%MIN1D=4, MIN2D=4, MIN3D=4, MIN4D=4%%''. Presently, values larger than 24 are not supported.
 +  * **''MPG''=//n//** Symmetry of the normal modes is recognized by the program automatically. Only Abelian point groups can be handled at the moment. Symmetry of the modes will be determined even if the ''NOSYM'' keyword is used in the electronic structure calculations. In certain cases numerical noise can be very high and thus prohibits a correct determination of the symmetry labels. Symmetry can be switched off by using ''MPG=1''.
 +  * **''NDIM''=//n//** The keyword ''NDIM=n'' terminates the expansion of the PES after the $n$-body term. Currently, at most 4-body terms can be included, but the default is set to 3. Please note, when you use ''NDIM=4'' as a keyword for the ''SURF'' program, you need to pass this information to the ''VSCF'' and ''VCI'' programs also. Otherwise these programs will neglect the 4-body terms.
 +  * **''NGRID''=//n//** Based on a coarse grid of //ab initio// points a fine grid will be generated from automated interpolation techniques. The keyword ''NGRID=n'' determines the number of equidistant grid points in one dimension. ''NGRID=n'' has to be an even number. The default is currently set to 16. Note that the number of grid points also controls the extension of the $n$-dimensional potential energy surfaces (see keyword ''SCALE'') and thus influences many internal thresholds which are optimized to the default value of ''NGRID''. The number of grid points also determines the number of basis functions in the grid-based ''VSCF'' program. At present the maximum grid size is 36.
  
-''BATCH3D''=//n// 
-After calculating a number of grid points within the iterative interpolation scheme the convergence of the individual surfaces will be checked and, if provided by the keyword ''DUMP'', dumped to disk. This leads typically to 3-5 iterations and thus the same number of restart points within the calculation of the 1D, 2D, ... surfaces. As the number of 3D and 4D terms can be very large this is not sufficient in these cases. Therefore, the lists of 3D and 4D terms is cut into batches which will be processed subsequently. ''BATCH3D'' and ''BATCH4D'' control the number of 3D and 4D surfaces within each batch. By default ''BATCH3D'' is set to 30 times the number of processors and ''BATCH4D'' to 10 times the number of processors. Accordingly the number of restart points is increased. Smaller values for ''BATCH3D'' and ''BATCH4D'', e.g. ''BATCH3D=20'', increase the number of restart points on cost of the efficiency of the parallelization. Note, this keyword is only relevant for ''SURF'' calculations, but not for ''XSURF'' runs. 
-''DELLOG''=//n// 
-For large molecules or in the case of modelling the 3D and 4D terms, the .log-file may become huge. First of all the .log-file can be directed to scratch within the electronic structure program, i.e. ''logfile'', ''scratch''. The option ''DELLOG=1'' always truncates the .log-file in a way that it contains only the very last energy calculation. Default: ''DELLOG=0''. 
-''EXT12D''=//value// 
-Outer regions of the potential energy surfaces may be determined by extrapolation rather than interpolation schemes. By default extrapolation is switched off, i.e. ''Ext12D=1.0'' and ''Ext34D=1.0''. However, an extrapolation of 10% in case of the 1D and 2D contributions to the potential (''Ext12D=0.9'') and of 20% in case of the 3D and 4D terms (''Ext34D=0.8'') may be useful as it usually stabilizes the fitting procedure. 
-''FIT1D''=//n// 
-The maximum order of the polynomials used for fitting within the iterative interpolation scheme can be controlled by the keywords ''%%FIT1D, FIT2D, FIT3D, FIT4D%%''. The default is given by 8. However in certain cases higher values may be necessary, but require an appropriate number of coarse grid points, which can be controlled by ''MIN1D'' etc. 
-''INFO''=//n// 
-''INFO=1'' provides a list of the values of all relevant program parameters (options). Default: ''INFO=0''. 
-''MAX1D''=//n// 
-The maximum number of coarse grid points can be controlled by the keywords ''%%MAX1D, MAX2D, MAX3D, MAX4D%%''. These 4 keywords determine the maximum number of //ab initio// calculations in one dimension for each 1D, 2D, 3D and 4D surface. The defaults are currently ''MAX1D=24'', ''MAX2D=16'', ''MAX3D=10'', ''MAX4D=8''. Presently, values larger than 24 are not supported. 
-''MIN1D''=//n// 
-The minimum number of coarse grid points can be controlled by the keywords ''%%MIN1D, MIN2D, MIN3D, MIN4D%%''. These 4 keywords determine the minimum number of //ab initio// calculations in one dimension for each 1D, 2D, 3D and 4D surface. The defaults are currently ''%%MIN1D=4, MIN2D=4, MIN3D=4, MIN4D=4%%''. Presently, values larger than 24 are not supported. 
-''MPG''=//n// 
-Symmetry of the normal modes is recognized by the program automatically. Only Abelian point groups can be handled at the moment. Symmetry of the modes will be determined even if the ''NOSYM'' keyword is used in the electronic structure calculations. In certain cases numerical noise can be very high and thus prohibits a correct determination of the symmetry labels. Symmetry can be switched off by using ''MPG=1''. 
-''NDIM''=//n// 
-The keyword ''NDIM=n'' terminates the expansion of the PES after the $n$-body term. Currently, at most 4-body terms can be included, but the default is set to 3. Please note, when you use ''NDIM=4'' as a keyword for the ''SURF'' program, you need to pass this information to the ''VSCF'' and ''VCI'' programs also. Otherwise these programs will neglect the 4-body terms. 
-''NGRID''=//n// 
-Based on a coarse grid of //ab initio// points a fine grid will be generated from automated interpolation techniques. The keyword ''NGRID=n'' determines the number of equidistant grid points in one dimension. ''NGRID=n'' has to be an even number. The default is currently set to 16. Note that the number of grid points also controls the extension of the $n$-dimensional potential energy surfaces (see keyword ''SCALE'') and thus influences many internal thresholds which are optimized to the default value of ''NGRID''. The number of grid points also determines the number of basis functions in the grid-based ''VSCF'' program. At present the maximum grid size is 36. 
 ^Grid points        ^   14     16     18     20   ^ ^Grid points        ^   14     16     18     20   ^
 |Surface extension  |  4.30  |  4.69  |  5.05  |  5.39  | |Surface extension  |  4.30  |  4.69  |  5.05  |  5.39  |
  
-''PLOT''=//n// +  * **''ORIENT''** Allows to specify a certain orientation of the molecule. With ''ORIENT=//yes//'' (Default) the orientation is choosed automatically according to the asymmetric parameter of the molecule. To choose a certain orientation, ''ORIENT=//XC//'' need to be set. X represents a number from 1 to 3 (in arabic or roman letters), and C need to be set to **r** or **l**. For example, ''ORIENT=//IIl//'' orientates the molecule according to the **IIl** convention. ''ORIENT=//old//'' does not rotate the molecule at all.  
-''PLOT''=//n// plots all //n//D surfaces and a corresponding Gnuplot script in a separate subdirectory (''plots1'') in the //home//-directory in order to allow for visualization of the computed //n//D surfaces. E.g. the command "gnuplot plotV1D.gnu" in the ''plots1'' directory produces .eps files for all 1D surfaces. Default: ''PLOT=0''+  * **''PLOT''=//n//** ''PLOT''=//n// plots all //n//D surfaces and a corresponding Gnuplot script in a separate subdirectory (''plots1'') in the //home//-directory in order to allow for visualization of the computed //n//D surfaces. E.g. the command "gnuplot plotV1D.gnu" in the ''plots1'' directory produces .eps files for all 1D surfaces. Default: ''PLOT=0''
-''SADDLE''=//n// +  * **''SADDLE''=//n//** Standard ''SURF'' calculations expect the reference structure to be a (local) minimum on the PES, i.e. ''SADDLE=0'' (default). Alternatively, one may start the PES generation from a transition state, which is recommended for the calculation of double-minimum potentials. This situation is not recognized automatically and thus requires the keyword ''SADDLE=1''. Within ''XSURF'' calculations, this keyword needs not to be provided. 
-Standard ''SURF'' calculations expect the reference structure to be a (local) minimum on the PES, i.e. ''SADDLE=0'' (default). Alternatively, one may start the PES generation from a transition state, which is recommended for the calculation of double-minimum potentials. This situation is not recognized automatically and thus requires the keyword ''SADDLE=1''. Within ''XSURF'' calculations, this keyword needs not to be provided. +  * **''SCALE''=//value//** The extension of the potential energy surfaces is determined from Gauss-Hermite quadrature points. Using a fine grid ''NGRID=16'' the surface stretches out to the ''NGRID''/2$^{th}$ Gauss-Hermite point, i.e. 4.69, in each direction (see keyword ''NGRID''). As these values are fairly large within the calculation of fundamental modes, a scaling factor, ''SCALE=f'', has been introduced. A default scaling of 0.75 is used. Increasing the size of the surfaces usually requires the calculation of further //ab initio// points as the surface interpolation is more stable for surfaces of limited size. Alternative to the ''SCALE'' option, which introduces a uniform scaling of all coordinates, individual scaling of the coordinates as provided by the directive ''SCALNM'' may be used. 
-''SCALE''=//value// +  * **''SKIP3D''=//value//** As the number of 3D and 4D surfaces can increase very rapidly, there exists the possibility to neglect unimportant 3D and 4D surfaces by the keywords ''SKIP3D'' and ''SKIP4D''. The criterion for the prescreening of the 3D surfaces is based on the 2D terms and likewise for the 4D terms the 3D surfaces are used. The neglect of 3D surfaces automatically leads to the neglect of 4D surfaces, as the latter depend on the previous ones. By default prescreening is switched on, but can be switched off by ''SKIP3D=0.0'' and ''SKIP4D=0.0''
-The extension of the potential energy surfaces is determined from Gauss-Hermite quadrature points. Using a fine grid ''NGRID=16'' the surface stretches out to the ''NGRID''/2$^{th}$ Gauss-Hermite point, i.e. 4.69, in each direction (see keyword ''NGRID''). As these values are fairly large within the calculation of fundamental modes, a scaling factor, ''SCALE=f'', has been introduced. A default scaling of 0.75 is used. Increasing the size of the surfaces usually requires the calculation of further //ab initio// points as the surface interpolation is more stable for surfaces of limited size. Alternative to the ''SCALE'' option, which introduces a uniform scaling of all coordinates, individual scaling of the coordinates as provided by the directive ''SCALNM'' may be used. +  * **''SYM''=//variable//** Symmetry within electronic structure calculations can be exploited by the keyword ''SYM=Auto''. Usually this leads to significant time savings. By default this symmetry recognition is switched off as certain calculations may cause some trouble (e.g. local correlation methods). Symmetry in electronic structure calculations may not be mistaken by the symmetry of the mode-coupling terms (see keyword ''MPG''). Once ''SYM=Auto'' is used, it is advisable to insert an ''INT'' card prior to the call of the Hartree-Fock program. 
-''SKIP3D''=//value// +  * **''THRFIT''=//value//** The iterative algorithm for generating potential energy surfaces is based on a successive increase of interpolation points. The iterations are terminated once the interpolation of two subsequent iteration steps became stable. The convergence threshold can be changed by the keyword ''THRFIT=f''. There is currently just one control variable for the different 1D, 2D, 3D, and 4D iterations. The 4 thresholds are different but depend on each other. Consequently, changing the default value (''THRFIT=4.0d-2'') will change all thresholds simultaneously which keeps the calculation balanced. 
-As the number of 3D and 4D surfaces can increase very rapidly, there exists the possibility to neglect unimportant 3D and 4D surfaces by the keywords ''SKIP3D'' and ''SKIP4D''. The criterion for the prescreening of the 3D surfaces is based on the 2D terms and likewise for the 4D terms the 3D surfaces are used. The neglect of 3D surfaces automatically leads to the neglect of 4D surfaces, as the latter depend on the previous ones. By default prescreening is switched on, but can be switched off by ''SKIP3D=0.0'' and ''SKIP4D=0.0''+  * **''TYPE''=//variable//** ''TYPE=QFF'' calls a macro, which modifies the parameters of the ''SURF'' program in order to compute a quartic force field in the most efficient manner. This implies a reduction of the size of the coupling surfaces and a limitation of the maximum number of points for the $n$D-terms. It should be used for VPT2 calculations. ''TYPE=ZPVE'' calls a macro, which changes the defaults for several parameters of the ''SURF'', ''VSCF'' and ''VCI'' programs. It is meant for the quick and efficient calculation of zero point vibrational energies on cost of some accuracy. For example, the expansion of the potential will be truncated after the 2D terms. As a consequence the output of course is reduced to the presentation of the vibrational ground state only. ''TYPE=FULL'' (default) performs a standard calculation as needed for ''VSCF'' or ''VCI'' calculations. Note that, within ''XSURF'' calculations, this keyword will be ignored, but Taylor expansions of the potential can be generated by using the ''VTAYLOR'' directive. 
-''SYM''=//variable// +  * **''USEMRCC''=//n//** Once the Mrcc program of M. Kallay or the Gecco program of A. Köhn is used for determining individual grid points, the option ''USEMRCC=1'' needs to be set, which is needed to ensure proper communication between Molpro and Mrcc. Default: ''USEMRCC=0''
-Symmetry within electronic structure calculations can be exploited by the keyword ''SYM=Auto''. Usually this leads to significant time savings. By default this symmetry recognition is switched off as certain calculations may cause some trouble (e.g. local correlation methods). Symmetry in electronic structure calculations may not be mistaken by the symmetry of the mode-coupling terms (see keyword ''MPG''). Once ''SYM=Auto'' is used, it is advisable to insert an ''INT'' card prior to the call of the Hartree-Fock program. +  * **''VAR1D''=//variable//** The ''SURF'' program reads the energy of electronic structure calculations from the internal Molpro variables, e.g. ''ENERGY'', ''EMP2'', $\dots$. The internal variable is specified by the keyword ''VAR1D''. Within the example shown above, ''VAR1D=ENERGY'' would read the CCSD energy, while ''VAR1D=EMP2'' would read the MP2 energy, which is a byproduct of the CCSD calculation. The default for the ''VAR1D'' keyword is the internal variable ''ENERGY''
-''THRFIT''=//value// +  * **''VRC''=//n//** Once the keyword ''VRC=1'' is provided, the ''SURF'' program will also compute the vibrational-rotational coupling surfaces and thus increases the number of degrees of freedom to 3N-3. Vibrational-rotational coupling surfaces can only be used within the ''PESTRANS'' program (see below), but will be neglected in any VSCF or VCI calculations.
-The iterative algorithm for generating potential energy surfaces is based on a successive increase of interpolation points. The iterations are terminated once the interpolation of two subsequent iteration steps became stable. The convergence threshold can be changed by the keyword ''THRFIT=f''. There is currently just one control variable for the different 1D, 2D, 3D, and 4D iterations. The 4 thresholds are different but depend on each other. Consequently, changing the default value (''THRFIT=4.0d-2'') will change all thresholds simultaneously which keeps the calculation balanced. +
-''TYPE''=//variable// +
-''TYPE=QFF'' calls a macro, which modifies the parameters of the ''SURF'' program in order to compute a quartic force field in the most efficient manner. This implies a reduction of the size of the coupling surfaces and a limitation of the maximum number of points for the $n$D-terms. It should be used for VPT2 calculations. ''TYPE=ZPVE'' calls a macro, which changes the defaults for several parameters of the ''SURF'', ''VSCF'' and ''VCI'' programs. It is meant for the quick and efficient calculation of zero point vibrational energies on cost of some accuracy. For example, the expansion of the potential will be truncated after the 2D terms. As a consequence the output of course is reduced to the presentation of the vibrational ground state only. ''TYPE=FULL'' (default) performs a standard calculation as needed for ''VSCF'' or ''VCI'' calculations. Note that, within ''XSURF'' calculations, this keyword will be ignored, but Taylor expansions of the potential can be generated by using the ''VTAYLOR'' directive. +
-''USEMRCC''=//n// +
-Once the Mrcc program of M. Kallay or the Gecco program of A. Köhn is used for determining individual grid points, the option ''USEMRCC=1'' needs to be set, which is needed to ensure proper communication between Molpro and Mrcc. Default: ''USEMRCC=0''+
-''VAR1D''=//variable// +
-The ''SURF'' program reads the energy of electronic structure calculations from the internal Molpro variables, e.g. ''ENERGY'', ''EMP2'', $\dots$. The internal variable is specified by the keyword ''VAR1D''. Within the example shown above, ''VAR1D=ENERGY'' would read the CCSD energy, while ''VAR1D=EMP2'' would read the MP2 energy, which is a byproduct of the CCSD calculation. The default for the ''VAR1D'' keyword is the internal variable ''ENERGY''+
-''VRC''=//n// +
-Once the keyword ''VRC=1'' is provided, the ''SURF'' program will also compute the vibrational-rotational coupling surfaces and thus increases the number of degrees of freedom to 3N-3. Vibrational-rotational coupling surfaces can only be used within the ''PESTRANS'' program (see below), but will be neglected in any VSCF or VCI calculations.+
  
 The following example shows the input of a calculation which computes energy and dipole surfaces at the MP2/cc-pVTZ level and subsequently determines the anharmonic frequencies at the VSCF and VCI levels. Hartree-Fock calculations will not be restarted and the .log-file is directed to the scratch directory as defined by the $TMPDIR variable. The following example shows the input of a calculation which computes energy and dipole surfaces at the MP2/cc-pVTZ level and subsequently determines the anharmonic frequencies at the VSCF and VCI levels. Hartree-Fock calculations will not be restarted and the .log-file is directed to the scratch directory as defined by the $TMPDIR variable.
Line 239: Line 220:
 Dipole surfaces can be computed for all those methods for which analytical gradients are available in Molpro. For all methods except Hartree-Fock this requires the keyword ''%%CPHF,1%%'' after the keyword for the electronic structure method. In multi-level schemes for which the variables ''VAR1D'', ''VAR2D'' and ''VAR3D'' are set individually, the VARDIP//n//D[X,Y,Z] variables have to be set accordingly. Symmetry is currently only implemented for the 1D, 2D and 3D dipole surfaces. For 4D terms symmetry will automatically switched off at the moment. The determination of dipole surfaces beyond Hartree-Fock quality effectively doubles the computation time for surface calculations. Dipole surfaces can be computed for all those methods for which analytical gradients are available in Molpro. For all methods except Hartree-Fock this requires the keyword ''%%CPHF,1%%'' after the keyword for the electronic structure method. In multi-level schemes for which the variables ''VAR1D'', ''VAR2D'' and ''VAR3D'' are set individually, the VARDIP//n//D[X,Y,Z] variables have to be set accordingly. Symmetry is currently only implemented for the 1D, 2D and 3D dipole surfaces. For 4D terms symmetry will automatically switched off at the moment. The determination of dipole surfaces beyond Hartree-Fock quality effectively doubles the computation time for surface calculations.
  
-Allows to switch between the different dipole surface calculations.=0 switches off all dipole calculations. ''DIPOLE''=1 (this is the default) computes the dipole surfaces at the Hartree Fock level of theory, and therefore does not increase the computation time of electronic structure theory. ''DIPOLE''=2 switches on the dipole surfaces at the full level of theory, therefore ''%%CPHF,1%%'' is required. This effectively doubles the computation time for surface calculations. +  * **''DIPOLE''=//n//** Allows to switch between the different dipole surface calculations.=0 switches off all dipole calculations. ''DIPOLE''=1 (this is the default) computes the dipole surfaces at the Hartree Fock level of theory, and therefore does not increase the computation time of electronic structure theory. ''DIPOLE''=2 switches on the dipole surfaces at the full level of theory, therefore ''%%CPHF,1%%'' is required. This effectively doubles the computation time for surface calculations. 
- +  * **''NDIMDIP''=//n//** This denotes the term after which the $n$-body expansion of the dipole surfaces is truncated. The default is set to 3. Note that ''NDIMDIP'' has to be lower or equal to ''NDIM''
-This denotes the term after which the $n$-body expansion of the dipole surfaces is truncated. The default is set to 3. Note that ''NDIMDIP'' has to be lower or equal to ''NDIM''+  * **''NDIMPOL''=//n//** This variable denotes the term after which the $n$-body expansion of the polarizability tensor surfaces is truncated. The default is set to 2. Note that ''NDIMPOL'' has to be lower or equal to ''NDIM'' and must be smaller than 4. 
- +  * **''POLAR''=//n//** By default (''POLAR''=0) Raman intensities will not be computed. ''POLAR''=1 switches the calculation of polarizability tensor surfaces on. Note that currently only Hartree-Fock and MP2 polarizabilities are supported, which requires the ''POLARI'' keyword in the respective programs. Besides that, the frozen core approximation cannot yet be employed within the calculation of MP2 polarizabilities. 
-This variable denotes the term after which the $n$-body expansion of the polarizability tensor surfaces is truncated. The default is set to 2. Note that ''NDIMPOL'' has to be lower or equal to ''NDIM'' and must be smaller than 4. +  * **''VARDIP1DX''=//variable//** Variable which is used for the $x$ direction of the dipole moment for 1D surfaces. 
- +  * **''VARDIP1DY''=//variable//** Variable which is used for the $y$ direction of the dipole moment for 1D surfaces. 
-By default (''POLAR''=0) Raman intensities will not be computed. ''POLAR''=1 switches the calculation of polarizability tensor surfaces on. Note that currently only Hartree-Fock and MP2 polarizabilities are supported, which requires the ''POLARI'' keyword in the respective programs. Besides that, the frozen core approximation cannot yet be employed within the calculation of MP2 polarizabilities. +  * **''VARDIP1DZ''=//variable//** Variable which is used for the $z$ direction of the dipole moment for 1D surfaces. 
- +  * **''VARPOL1DXX''=//variable//** Variable which is used for the $xx$ component of the polarizability tensor for 1D surfaces. 
-Variable which is used for the $x$ direction of the dipole moment for 1D surfaces. +  * **''VARPOL1DYY''=//variable//** Variable which is used for the $yy$ component of the polarizability tensor for 1D surfaces. 
- +  * **''VARPOL1DZZ''=//variable//** Variable which is used for the $zz$ component of the polarizability tensor for 1D surfaces. 
-Variable which is used for the $y$ direction of the dipole moment for 1D surfaces. +  * **''VARPOL1DXY''=//variable//** Variable which is used for the $xy$ component of the polarizability tensor for 1D surfaces. 
- +  * **''VARPOL1DXZ''=//variable//** Variable which is used for the $xz$ component of the polarizability tensor for 1D surfaces. 
-Variable which is used for the $z$ direction of the dipole moment for 1D surfaces. +  * **''VARPOL1DYZ''=//variable//** Variable which is used for the $yz$ component of the polarizability tensor for 1D surfaces.
- +
-Variable which is used for the $xx$ component of the polarizability tensor for 1D surfaces. +
- +
-Variable which is used for the $yy$ component of the polarizability tensor for 1D surfaces. +
- +
-Variable which is used for the $zz$ component of the polarizability tensor for 1D surfaces. +
- +
-Variable which is used for the $xy$ component of the polarizability tensor for 1D surfaces. +
- +
-Variable which is used for the $xz$ component of the polarizability tensor for 1D surfaces. +
- +
-Variable which is used for the $yz$ component of the polarizability tensor for 1D surfaces.+
  
 The higher order terms VARDIP//n//D[X,Y,Z] and VARPOL//n//D[XX,$\dots$,YZ] can be defined the same way. An example for a calculation, which provides both, infrared and Raman intensities, is given below. The higher order terms VARDIP//n//D[X,Y,Z] and VARPOL//n//D[XX,$\dots$,YZ] can be defined the same way. An example for a calculation, which provides both, infrared and Raman intensities, is given below.
Line 323: Line 292:
 The ''SCALE'' option of the ''SURF'' program enables a modification of the extension of all difference potentials by a common factor. In contrast to that the ''SCALNM'' directive allows for the scaling with respect to the individual normal coordinates. This is the recommended choice for potentials dominated by quartic rather than quadratic terms. At most 3N-6 individual scale factors and shift parameters can be provided. In particular the ''AUTO'' option was found to be very helpful in practical applications. The ''SCALE'' option of the ''SURF'' program enables a modification of the extension of all difference potentials by a common factor. In contrast to that the ''SCALNM'' directive allows for the scaling with respect to the individual normal coordinates. This is the recommended choice for potentials dominated by quartic rather than quadratic terms. At most 3N-6 individual scale factors and shift parameters can be provided. In particular the ''AUTO'' option was found to be very helpful in practical applications.
  
-  * **''AUTO''=//on / off//** ''AUTO''=//on// (defaulr) switches on an automatic scaling procedure of the potential in order to determine meaningful elongations and ''SHIFT'' values with respect to all coordinates, i.e. for each normal mode an optimized scaling parameter ''SFAC'' and ''SHIFT'' parameter will be determined. Usually this results in an increased number of 1D grid points. The ''AUTO'' keyword intrinsically depends on the thresholds and parameters, which can be controlled by the keywords ''THRSHIFT'', ''ITMAX'', ''LEVMAX'', ''DENSMAX'', and ''DENSMIN''.+  * **''AUTO''=//on / off//** ''AUTO''=//on// (default) switches on an automatic scaling procedure of the potential in order to determine meaningful elongations and ''SHIFT'' values with respect to all coordinates, i.e. for each normal mode an optimized scaling parameter ''SFAC'' and ''SHIFT'' parameter will be determined. Usually this results in an increased number of 1D grid points. The ''AUTO'' keyword intrinsically depends on the thresholds and parameters, which can be controlled by the keywords ''THRSHIFT'', ''ITMAX'', ''LEVMAX'', ''DENSMAX'', and ''DENSMIN''.
   * **''DENSMAX''=//value//** Threshold for the maximum vibrational density on the edges of the potential needed for the automated upscaling of the potentials (see keyword ''AUTO'').   * **''DENSMAX''=//value//** Threshold for the maximum vibrational density on the edges of the potential needed for the automated upscaling of the potentials (see keyword ''AUTO'').
   * **''DENSMIN''=//value//** Threshold for the minimum vibrational density on the edges of the potential needed for the automated downscaling of the potentials (see keyword ''AUTO'').   * **''DENSMIN''=//value//** Threshold for the minimum vibrational density on the edges of the potential needed for the automated downscaling of the potentials (see keyword ''AUTO'').
Line 492: Line 461:
  
  
-[\tt Problem:]+**Problem:**
 The Surf calculation crashes with an error message like The Surf calculation crashes with an error message like
 <code> <code>
Line 499: Line 468:
  CURRENT STACK:      MAIN  CURRENT STACK:      MAIN
 </code> </code>
-[\tt Solution:]+ 
 +**Solution:**
 The program has problems in the symmetry conversion when restarting a Hartree-Fock calculation from the reference calculation at the equilibrium geometry. You need to start the Hartree-Fock calculations independently by using the keywords ''%%start,atden%%''. The program has problems in the symmetry conversion when restarting a Hartree-Fock calculation from the reference calculation at the equilibrium geometry. You need to start the Hartree-Fock calculations independently by using the keywords ''%%start,atden%%''.
  
  
-[\tt Problem:]+**Problem:**
 In parallel calculations (mppx) the CPU-time of a ''SURF'' calculation differs considerably from the real-time (wallclock time). In parallel calculations (mppx) the CPU-time of a ''SURF'' calculation differs considerably from the real-time (wallclock time).
-[\tt Solution:]+ 
 +**Solution:**
 There may be two reasons for this: (1) Usually a ''SURF'' calculation spends a significant amount of the total time in the Hartree-Fock program and the 2-electron integrals program. As the integrals are stored on disk, 2 processes on the same machine may write on disk at the same time and thus the calculation time depends to some extend on the disk controller. It is more efficient to stripe several disks and to use several controllers. This problem can be circumvented by distributing the job over several machines, but limiting the number of processors for each machine to 1. (2) The integrals program buffers the integrals. Parallel jobs may require too much memory (factor of 2 plus the shared memory) and thus the integrals buffering will be inefficient. Try to reduce the memory as much as you can. It might be advantageous to separate the memory demanding ''VCI'' calculation from the ''SURF'' calculation. There may be two reasons for this: (1) Usually a ''SURF'' calculation spends a significant amount of the total time in the Hartree-Fock program and the 2-electron integrals program. As the integrals are stored on disk, 2 processes on the same machine may write on disk at the same time and thus the calculation time depends to some extend on the disk controller. It is more efficient to stripe several disks and to use several controllers. This problem can be circumvented by distributing the job over several machines, but limiting the number of processors for each machine to 1. (2) The integrals program buffers the integrals. Parallel jobs may require too much memory (factor of 2 plus the shared memory) and thus the integrals buffering will be inefficient. Try to reduce the memory as much as you can. It might be advantageous to separate the memory demanding ''VCI'' calculation from the ''SURF'' calculation.
  
Line 520: Line 491:
 ==== Options ==== ==== Options ====
  
 +    **''AUTOFIT''=//n//** (=0 Default) If ''AUTOFIT''=1, the number of basis function for fitting the grid points is determined automatically. To do so, the fine grid of the energy is compared to the coarse grid points. If the deviation is too high, another basis function is added. The procedure starts with 8 basis functions and stops at the latest at ''FITXD_MAX'' basis functions. Once 'AUTOFIT' is used, the keywords ''FITXD'' does not have any use.
   * **''CORRECT''=//n//** (=1 (on) Default) If a certain subsurface does not converge despite increasing the number of ab initio calculations, symmetry in this subsurface (if any) will be neglected in order to avoid any errors due to inaccuracies in the displacement vectors and the subsurface will be recalculated accordingly. This option is automatically switched off in any Taylor expansions of the PES.   * **''CORRECT''=//n//** (=1 (on) Default) If a certain subsurface does not converge despite increasing the number of ab initio calculations, symmetry in this subsurface (if any) will be neglected in order to avoid any errors due to inaccuracies in the displacement vectors and the subsurface will be recalculated accordingly. This option is automatically switched off in any Taylor expansions of the PES.
 +  * **''FITXD_MAX''=//n//**(=10 Default) For the automated procedure with ''AUTOFIT'' an upper limit for the number of basis functions can be set with this keyword.
   * **''FITMETHOD''=//n//** (=1 Default) Within the iterative build-up of the individual subsurfaces, intermediate fitting will be used. This can be based on true multidimensional Kronecker product fitting (''FITMETHOD''=1) or on fitting along one-dimensional cuts (''FITMETHOD''=2).   * **''FITMETHOD''=//n//** (=1 Default) Within the iterative build-up of the individual subsurfaces, intermediate fitting will be used. This can be based on true multidimensional Kronecker product fitting (''FITMETHOD''=1) or on fitting along one-dimensional cuts (''FITMETHOD''=2).
   * **''INFO''=//n//** (=1 Default) ''INFO''=0 suppresses any information about the program parameters and symmetry information. ''INFO''=1 refers to the standard output, while ''INFO''=2 provides additional information about the symmetry recognition.   * **''INFO''=//n//** (=1 Default) ''INFO''=0 suppresses any information about the program parameters and symmetry information. ''INFO''=1 refers to the standard output, while ''INFO''=2 provides additional information about the symmetry recognition.
Line 540: Line 513:
   * **''THRSED''=//value//** (=1.0d-6 Default) Threshold for determining symmetry elements of the molecule.   * **''THRSED''=//value//** (=1.0d-6 Default) Threshold for determining symmetry elements of the molecule.
   * **''THRSYMx''=//value//** ($x$=1,2,...) Threshold used for recognizing symmetry within a subsurface of the PES expansion - in dependence on the order of the expansion term. The defaults are ''THRSYM1''=5.0d-5, ''THRSYM2''=1.0d-5,''THRSYM3''=5.0d-6,''THRSYM4''=5.0d-6,''THRSYM5''=1.0d-7.   * **''THRSYMx''=//value//** ($x$=1,2,...) Threshold used for recognizing symmetry within a subsurface of the PES expansion - in dependence on the order of the expansion term. The defaults are ''THRSYM1''=5.0d-5, ''THRSYM2''=1.0d-5,''THRSYM3''=5.0d-6,''THRSYM4''=5.0d-6,''THRSYM5''=1.0d-7.
 +  * **''DELAUTO''=//variable//**(=//off// Default) If ''DELAUTO''=//on//, all not converged surfaces of the highest considered dimension are deleted. It only works after a restart from an external potfile.
  
 +==== Selection of Modes ====
 +''VIBMODE'',//options//
 +
 +The ''VIBMODE'' directive allows to span the PES only with predefined modes. The following options can be combined in various ways.
 +
 +  * **''ENERGHIGH''=//x//** Modes with a frequency lower than **x** are used to span the surface (according to the harmonic frequencies)
 +  * **''ENERGLOW''=//x//** Modes with a frequency higher than **x** are used to span the surface (according to the harmonic frequencies)
 +  * **''HIGH''=//n//** the highest **n** modes are used to span the surface
 +  * **''LOW''=//n//** the lowest **n** modes are used to span the surface
 +  * **''MODE''=//n//** Mode which is used to span the surface (can be used multiple times)
 ==== Visualisation and interfaces ==== ==== Visualisation and interfaces ====
  
Line 745: Line 729:
 The ''INTERFACE'' directive allows for the communication with other programs. It writes information about the individual grid points of a PES to an external ASCII file, which can be processed by other software. Likewise, files in the same structure with additional information from external programs can be read in. After reading in all data points, the date points will be transformed into a fine grid and fitted to polynomials. The ''INTERFACE'' directive allows for the communication with other programs. It writes information about the individual grid points of a PES to an external ASCII file, which can be processed by other software. Likewise, files in the same structure with additional information from external programs can be read in. After reading in all data points, the date points will be transformed into a fine grid and fitted to polynomials.
  
- +  * **''COPY''=//n//** (=0 Default) Once new data have been generated in the external ASCII file, the coefficients of the corresponding polynomials can be displayed in the ''POLY'' program using the option ''COEF_INTERFACEx'' with (x=1,2...). It is also possible to replace the energy or dipole surfaces generated by Molpro by these new quantities by ''COPY=ENE'' or ''COPY=DIP''
-''COPY''=//n// +  * **''DATA''=//n//** (=1 Default) ''DATA=1'' provides detailed information about each single point of the PES in a formatted output. ''DATA=2'' provides the geometry and energy of a given point in a single line. New information about this point needs to be added at the end of the line. ''DATA=2'' prints the displacements along the coordinates and the energy in a single line. Again, new information needs to be added at the end of this line. 
-(=0 Default) Once new data have been generated in the external ASCII file, the coefficients of the corresponding polynomials can be displayed in the ''POLY'' program using the option ''COEF_INTERFACEx'' with (x=1,2...). It is also possible to replace the energy or dipole surfaces generated by Molpro by these new quantities by ''COPY=ENE'' or ''COPY=DIP''+  * **''NDIM''=//n//** (=0 Default) Dimension of the $n$-mode expansion to which the geometry information shall be dumped. 
-''DATA''=//n// +  * **''NRES''=//n//** (=1 Default) Number of columns being added to the external file by an external program. 
-(=1 Default) ''DATA=1'' provides detailed information about each single point of the PES in a formatted output. ''DATA=2'' provides the geometry and energy of a given point in a single line. New information about this point needs to be added at the end of the line. ''DATA=2'' prints the displacements along the coordinates and the energy in a single line. Again, new information needs to be added at the end of this line. +  * **''SURFACE''=//n//** (=0 Default) Information about the energy values printed in the external file. ''SURFACE=0'' refers to absolute energies (minus the reference energy), while ''SURFACE=1'' refers to energy differences belonging to the individual increments of the subsurfaces. 
-''NDIM''=//n// +  * **''TYPE''=//variable//** (=OUT Default) This option controls, if the file shall be written ''TYPE=OUT'' or read in ''TYPE=IN''
-(=0 Default) Dimension of the $n$-mode expansion to which the geometry information shall be dumped. +  * **''ZERO''=//n//** (=1 Default) If set to 1, geometries of lower orders of the $n$-mode representation will be printed, i.e. the external file contains redundand data. ''ZERO=0'' neglects all redundancies and prints only unique points. As a consequence, an external file generated this way cannot be read in again for technical reasons. 
-''NRES''=//n// +  * **''WFU''=//file name//** Specifies the name of the external file.
-(=1 Default) Number of columns being added to the external file by an external program. +
-''SURFACE''=//n// +
-(=0 Default) Information about the energy values printed in the external file. ''SURFACE=0'' refers to absolute energies (minus the reference energy), while ''SURFACE=1'' refers to energy differences belonging to the individual increments of the subsurfaces. +
-''TYPE''=//variable// +
-(=OUT Default) +
-This option controls, if the file shall be written ''TYPE=OUT'' or read in ''TYPE=IN''+
-''ZERO''=//n// +
-(=1 Default) If set to 1, geometries of lower orders of the $n$-mode representation will be printed, i.e. the external file contains redundand data. ''ZERO=0'' neglects all redundancies and prints only unique points. As a consequence, an external file generated this way cannot be read in again for technical reasons. +
-''WFU''=//file name// +
-Specifies the name of the external file.+
  
 ==== Grid computing interface ==== ==== Grid computing interface ====
Line 774: Line 748:
   * **''MEMORY''=//n//** Memory request of the individual single point calculations in MW.   * **''MEMORY''=//n//** Memory request of the individual single point calculations in MW.
   * **''WFU''=//file name//** If additional information need to be read in from a .wfu file, this can be specified here.   * **''WFU''=//file name//** If additional information need to be read in from a .wfu file, this can be specified here.
 +