DESCRIPTION

The program input is a preliminary program which reads the input data for the molecule (geometry, basis set, etc. ) and generates a working file called which is the real starting point of each calculation. The input program can handle a total of 100 atoms and 1500 unique primitive gaussian functions. The input program limits the use of symmetry point groups to D2h and its subgroups.

REFERENCES

For STO basis sets:

1.

W. J. Hehre, R. F. Stewart and J.A. Pople, J. Chem. Phys. 51 (1969) 2657.

2.

W. J. Hehre, R. Ditchfield, R. F. Stewart and J.A. Pople, J. Chem. Phys. 52 (1970) 2769.

For DZ and the old TZ basis sets:

1.

S. Huzinaga, J. Chem. Phys. 42 (1965) 1293.

2.

T. H. Dunning, J. Chem. Phys. 53 (1970) 2823.

For DZP basis sets:
  for Li and Be;

1.

A. J. Thakkar, T. Koga, M. Saito, R. E. Hoffmeyer, Inter. J. Quant. Chem. Symp. 27 (1993) 343.

  for Na and Mg;

1.

S. Huzinaga, Approximate Atomic Wavefunction II, Dept. of Chem. Report, Univ. of Alberta, Edmonton, Alberta, Canada, 1971.

For the Rydberg and negative ion basis sets:

1.

T. H. Dunning, Jr. and P. J. Hay, in Modern Theoretical Chemistry, Volume 3, Ed. H. F. Schaefer III, Plenum Press, NY, 1977.

For the new TZ basis sets:

1.

T. H. Dunning, J. Chem. Phys. 55, (1971) 716.

2.

A. D. McLean and G. S. Chandler, J. Chem. Phys., 72 (1980) 5639.

For the general contracted basis sets:

1.

T. H. Dunning Jr., J. Chem. Phys. 90, (1989).

2.

F. B. van Duijneveldt, IBM Res. Rep. RJ 945 (1971).

For the Wachters basis sets:

1.

A. J. H. Wachters, J. Chem. Phys. 52, (1970) 1033.

For the cc-pVXZ (X=D,T,Q) basis sets for hydrogen and the
  first row atoms B-Ne:

1.

T.H. Dunning, Jr., J. Chem. Phys. 90, 1007 (1989).

For the aug-cc-pVXZ (X=D,T,Q) basis sets for H and B-Ne:

1.

R.A. Kendall, T.H. Dunning, Jr., and R.J. Harrison, J. Chem. Phys. 96, 6796 (1992).

For the cc-pVXZ and aug-cc-pVXZ (X=D,T,Q) sets for the
  second row atoms Al-Ar:

1.

D.E. Woon and T.H. Dunning, Jr., J. Chem. Phys. 98, 1358 (1993).

For the cc-pVXZ (X=D,T,Q) basis sets for helium; cc-pV5Z and
  aug-cc-pV5Z basis sets for H, B-Ne, and Al-Ar:

1.

D.E. Woon, K.A. Peterson, and T.H. Dunning, Jr. (unpublished).

For the cc-pVXZ and aug-cc-pVXZ (X=D,T,Q) basis sets for
  lithium, beryllium, and sodium; cc-pV5Z and aug-cc-pV5Z
  basis sets for beryllium:

1.

D.E. Woon and T.H. Dunning, Jr. (unpublished).

Also see

1.

R. Poirier, R. Kari and I. G. Csizmadia, "Handbook of Gaussian Basis Sets" Phys. Sci. Data 24 (Elsevier, 1985), and references therein.

INPUT FORMAT

In addition to the standard command-line options supported by all Psi 3 modules, the following command-line arguments are available:

--keep_chkpt

This option will cause input to keep the checkpoint file and possibly overwrite the information. By default, input will delete the checkpoint file and create a new one.

--chkptgeom

This option will cause input to read the geometry from checkpoint file rather than from the input file.

--chkptmos

This option will cause INPUT to try to recover molecular orbitals from a previous calculation archived in the checkpoint file. If found, occupied MOs will be projected onto the new basis. The virtual space is filled up by the virtual MOs obtained by diagonalizing the core Hamiltonian (even if the new and old basis sets are identical). This will not affect the subsequent SCF procedure in any way, but should be kept in mind.

--noproject

This option will prevent projection of MOs onto the new basis. Useful in combination with the previous option.

--noreorient

This option will prevent the reorientation of the molecule to the reference inertia frame prior to the determination of the point group.

--nocomshift

This option will prevent shift of the center of mass of the molecule to the origin prior to the determination of the point group.

--savemos

This option will cause INPUT to try to recover molecular orbitals from a previous calculation archived in the checkpoint file. If found, the SCF eigenvector and other information will be stored to file 42.

The input program searches through the default keyword path (first INPUT and then DEFAULT) for the following keywords:

LABEL = string

This is a descriptive label for the calculation. There is no default.

NORMBASIS = boolean

If NORMBASIS=YES, the molecular orbital coefficients of the occupied orbitals are given in terms of normalized contracted basis functions. This should always be true. The default is true.

PRIMNORM = boolean

If PRIMNORM=YES, the contraction coefficients of the D, F, and G primitive functions that are input should be the ones corresponding to the normalized D(XX), F(XXX) and G(XXXX) primitives. All of the basis sets provided with Psi require that this be true. The default is true.

SUBGROUP = string

This is the subgroup to be used in the calculation. For the C1 point group use string = C1; for Cs use CS; for Ci use CI; for C2 use C2; for C2h use C2H; for C2v use C2V; and for D2 use D2; There is no default.

UNIQUE_AXIS = string

This keyword specifies which axis in the original (before the principal axis reorientation) coordinate system should be chosen as the unique axis in the subgroup specification. For example, if one wants to perform a calculation on a D2h molecule in C2v symmetry, one has to specify which of the three C2 axes has to serve as the unique axis. There's no default.

UNITS = string

If string is BOHR, then the GEOMETRY array is in bohr. If string is ANGSTROM, then the GEOMETRY array is in angstoms. The default is BOHR.

GEOMETRY = array

The array is a vector of cartesian coordinates of EACH atom. Each element of this vector is another vector in the form ( atom_name x y z). There is no default.

ZMAT = array

The array is a Z-matrix for the molecule. Each element of this vector is another vector in the general form ( atom_name atom1 bond_distance atom2 valence_angle atom3 torsional_angle). The first three atoms don't require all of the parameters to be specified There is no default.

PUREAM = boolean

If boolean is TRUE, then shells with pure angular momentum will be used. Thus, a D shell will have five function, a F shell will have seven functions, a G shell will have nine functions, etc. The default is false.

BASIS = string/string_vector

If basis set is given as a single string, the same basis set will be used for all atoms. Basis set for EACH atom can be specified in a one-dimensional string vector, however, user must be careful, since only basis sets for unique atoms will be read from the vector. Basis set for each element type can be specified analogously, however each element of the basis set vector must be a vector consisting of two elements: element name and basis set name. There is no default.

BASIS_FILE = string

This keyword specifies the name of an alternate file to be searched for basis set information. Either an absolute path to the file or a path relative to the current directory can be used. If the string is terminated by "/" (only directory is specified) then the default file name "basis.dat" will be appended.

NO_REORIENT = boolean

This keyword is a hack to give user more control in certain situations when reorientation into the principal frame leaves some symmetry elements undetected. When set to TRUE, the program will skip this reorientation step. The user then becomes responsible for providing an initial orientation that is oriented properly for all symmetry elements to be detected. This can be tricky with Z-matrices, hence only experts should use this keyword.

KEEP_REF_FRAME = boolean

When this keyword is set to true Psi will keep track of the original coordinate frame, i.e. the coordinate frame right after the center of mass shift and before the reorientation into the principal frame. That frame is called reference frame and, in general, is different from the canonical coordinate frame adopted at the end of input run and used for computations by all Psi modules programs henceforth. The information about the reference frame thus need to be stored in the checkpoint file if Psi modules (such as CINTS) need to transform their frame-dependent results (such as forces on the nuclei) into the original reference frame for external programs to use. This keyword becomes useful in finite difference computations where changes in point group may cause the molecule to reorient - when KEEP_REF_FRAME is set to TRUE all gradients in FILE11 will be printed in the same coordinate frame.

PRINT = integer

This controls the amount of information to be printed out. The greater the number - the more information gets printed. Default (PRINT = 1) should be enough for routine use.

BASIS SETS

The input program searches through the BASIS keyword path for the basis set information. It first searches through the user's file, then searches through a file in the working directory (if one exists), and then through a user specified basis file specified by the BASIS_FILE keyword (if any). Finally, it searches through the file in the Psi library directory. The name of the basis set which is searched for is obtained by appending the atom name to the basis name with a ':' inbetween. The format of the basis set information is best understood by looking in the file.

STANDARD BASIS SETS

Psi can use use standard basis sets which are provided in a file named in the Psi library directory. Many of the basis set names contain nonalphanumeric characters. These names must be surrounded by `"'.

STO

This gets the STO-3G basis set which is available for hydrogen-argon. The STO-3G basis sets for the atoms sodium-argon contain a D function.

DZ

This gets double zeta (DZ) basis set, which is (4s/2s) for hydrogen, (9s5p/4s2p) for boron-fluorine, and (11s7p/6s4p) for aluminum-chlorine.

(4S/2S)

This gets a DZ basis set for hydrogen.

(9S5P/4S2P)

This gets a DZ basis set for boron-fluorine.

(11S7P/6S4P)

This gets a DZ basis set for aluminum-chlorine.

DZP-OLD

This is a DZ basis set with a shell of polarization functions added. The exponents of these functions are the old value. It is available for hydrogen, boron-fluorine, and aluminum-chlorine.

TZ-OLD

The old triple zeta (TZ) basis set is (4s/3s) for hydrogen, (9s5p/5s3p) for boron-fluorine, and (11s7p/7s5p) for aluminum-chlorine. The TZ basis set is triple zeta in the valence only. This basis is provided for verification of old results; do not use it.

TZP-OLD

This is the old TZ basis set with the old polarization functions added. It is available for hydrogen, boron-fluorine, and aluminum-chlorine. This basis is provided for verification of old results; do not use it.

(5S/3S)

This gets a TZ basis set for hydrogen.

(10S6P/5S3P)

This gets a TZ basis set for boron-neon. The TZ basis set is triple zeta in the valence only.

(12S9P/6S5P)

This gets a TZ basis set for sodium-argon. The TZ basis set is triple zeta in the valence only.

1P_POLARIZATION

This gets a set of polarization functions for hydrogen.

1D_POLARIZATION

This gets a set of polarization functions for boron-fluorine and aluminum-chlorine.

2P_POLARIZATION

This gets two sets of polarization functions for hydrogen.

2D_POLARIZATION

This gets two sets of polarization functions for boron-fluorine and aluminum-chlorine.

1D_POLARIZATION

This gets a set of second polarization functions for hydrogen.

1F_POLARIZATION

This gets a set of second polarization functions for boron-fluorine and aluminum-chlorine.

DZP

This gets a (4S/2S) basis with a "1P_POLARIZATION" function for hydrogen, a (9S5P/4S2P) basis with a "1D_POLARIZATION" funtion for lithium-flourine, a (11S5P/7S2P) plus two even-tempered p functions for sodium and magnesium, and a (11S7P/6S4P) basis with a "1D_POLARIZATION" function for aluminium-chlorine.

TZ2P

This gets a (5S/3S) basis with "2P_POLARIZATION" functions for hydrogen, a (10S6P/5S3P) basis with "2D_POLARIZATION" funtions for boron-flourine, and a (12S9P/6S5P) basis with "2D_POLARIZATION" functions for aluminium-chlorine.

DZ_DIF

This gets a DZ basis with a diffuse s for hydrogen, and a diffuse s and diffuse p for boron-flourine, and aluminum-chlorine.

TZ_DIF

This gets a TZ basis with a diffuse s for hydrogen, and a diffuse s and diffuse p for boron-flourine, and aluminum-chlorine.

DZP_DIF

This gets the DZP basis with a diffuse s for hydrogen, and a diffuse s and diffuse p for boron-flourine, and aluminum-chlorine.

TZ2P_DIF

This gets the TZ2P basis with a diffuse s for hydrogen, and a diffuse s and diffuse p for boron-flourine, and aluminum-chlorine.

TZ2PF

This gets the TZ2P basis and adds "1D_POLARIZATION" for hydrogen and "1F_POLARIZATION" for boron-flourine, and aluminum-chlorine.

TZ2PD

This gets the TZ2PF basis set for hydrogen.

TZ2PF_DIF

This gets a TZ2PF basis and adds the appropriate s diffuse functions for hydrogen and s and p diffuse functions for boron-flourine, and aluminum-chlorine.

CCPVDZ

This gets the segmentally contracted correlation consistent basis set cc-pVDZ, which is (4s1p/2s1p) for hydrogen and helium, (9s4p1d/3s2p1d) for lithium - neon, and (12s8p1d/4s3p1d) for sodium and aluminum - argon.

CCPVTZ

This gets the segmentally contracted correlation consistent basis set cc-pVTZ, which is (5s2p1d/3s2p1d) for hydrogen and helium, (10s5p2d1f/4s3p2d1f) for lithium - neon, and (15s9p2d1f/5s4p2d1f) for sodium and aluminum - argon.

CCPVQZ

This gets the segmentally contracted correlation consistent basis set cc-pVQZ, which is (6s3p2d1f/4s3p2d1f) for hydrogen and helium, (12s6p3d2f1g/5s4p3d2f1g) for lithium - neon, and (16s11p3d2f1g/6s5p3d2f1g) for sodium and aluminum - argon.

CCPV5Z

This gets the segmentally contracted correlation consistent basis set cc-pV5Z, which is (8s4p3d2f1g/5s4p3d2f1g) for hydrogen and helium, (14s8p4d3f2g1h/6s5p4d3f2g1h) for beryllium - neon, and (20s12p4d3f2g1h/7s6p4d3f2g1h) for aluminum - argon.

PLEASE NOTE: The correlation consistent basis sets cc-pVXZ (X = D, T, Q, 5) are designed for use with pure angular momentum functions.

AUGCCPVDZ

This gets the correlation consistent basis set aug-cc-pVDZ, which is the cc-pVDZ basis set augmented with optimized diffuse functions. This is a diffuse (1s1p) set for hydrogen and helium and a diffuse (1s1p1d) set for lithium - neon, sodium, and aluminum - argon.

AUGCCPVTZ

This gets the correlation consistent basis set aug-cc-pVTZ, which is the cc-pVTZ basis set augmented with optimized diffuse functions. This is a diffuse (1s1p1d) set for hydrogen and helium and a diffuse (1s1p1d1f) set for lithium - neon, sodium, and aluminum - argon.

AUGCCPVQZ

This gets the correlation consistent basis set aug-cc-pVQZ, which is the cc-pVQZ basis set augmented with optimized diffuse functions. This is a diffuse (1s1p1d1f) set for hydrogen and helium and a diffuse (1s1p1d1f1g) set for lithium - neon, sodium, and aluminum - argon.

AUGCCPV5Z

This gets the correlation consistent basis set aug-cc-pV5Z, which is the cc-pV5Z basis set augmented with optimized diffuse functions. This is a diffuse (1s1p1d1f1g) set for hydrogen and helium and a diffuse (1s1p1d1f1g1h) set for beryllium - neon and aluminum - argon.

GCVDZ

A general contracted basis set for hydrogen, for which it is (4s)/[2s], and for boron-neon for which it is (9s4p)/[3s2p].

GCVTZ

A general contracted basis set for hydrogen, for which it is (5s)/[3s], and for boron-neon for which it is (10s5p)/[4s3p].

GCVQZ

A general contracted basis set for hydrogen, for which it is (6s)/[4s], and for boron-neon for which it is (12s6p)/[5s4p].

GCV1P

This gets one P polarization shell for hydrogen (for use with GCVDZ).

GCV2P

This gets two P polarization shells for hydrogen (for use with GCVTZ).

GCV3P

This gets three P polarization shells for hydrogen (for use with GCVQZ).

GCV1D

This gets one D polarization shell for hydrogen (for use with GCVTZ) and boron-neon (for use with GCVDZ).

GCV2D

This gets two D polarization shells for hydrogen (for use with GCVQZ) and boron-neon (for use with GCVTZ).

GCV3D

This gets three D polarization shells for boron-neon (for use with GCVQZ).

GCV1F

This gets one F polarization shell for hydrogen (for use with GCVQZ) and boron-neon (for use with GCVTZ).

GCV2F

This gets two F polarization shells for boron-neon (for use with GCVQZ).

GCV1G

This gets one G polarization shell for boron-neon (for use with GCVQZ).

GCV1DPURE

This is GCV1D with pure angular momentum explicitly turned on.

GCV2DPURE

This is GCV2D with pure angular momentum explicitly turned on.

GCV3DPURE

This is GCV3D with pure angular momentum explicitly turned on.

GCV1FPURE

This is GCV1F with pure angular momentum explicitly turned on.

GCV2FPURE

This is GCV2F with pure angular momentum explicitly turned on.

GCV1GPURE

This is GCV1G with pure angular momentum explicitly turned on.

GCVDZP

A general contracted basis set for hydrogen, for which it is (4s1p)/[2s1p], and for boron-neon, for which it is (9s4p1d)/[3s2p1d].

GCVTZP

A general contracted basis set for hydrogen, for which it is (5s2p1d)/[3s2p1d], and for boron-neon, for which it is (10s5p2d1f)/[4s3p2d1f].

GCVQZP

A general contracted basis set for hydrogen, for which it is (6s3p2d1f)/[4s3p2d1f], and for boron-neon for which it is (12s6p3d2f1g)/[5s4p3d2f1g].

DUNNING_RYDBERG_3S

This gets a Rydberg shell for boron-fluorine.

DUNNING_RYDBERG_3P

This gets a Rydberg shell for boron-fluorine.

DUNNING_RYDBERG_3D

This gets a Rydberg shell for boron-fluorine and aluminum-chlorine.

DUNNING_RYDBERG_4S

This gets a Rydberg shell for boron-fluorine and aluminum-chlorine.

DUNNING_RYDBERG_4P

This gets a Rydberg shell for boron-fluorine and aluminum-chlorine.

DUNNING_RYDBERG_4D

This gets a Rydberg shell for boron-fluorine.

DUNNING_NEGATIVE_ION_2P

This gets a diffuse shell for boron-fluorine and aluminum-chlorine.

WACHTERS

This gets a (14s11p6d/10s8p3d) basis set for potassium,scandium-zinc.

321G

This gets a 3-21G basis set for hydrogen-argon.

631G

This gets a 6-31G basis set for hydrogen-argon.

6311G

This gets a 6-311G basis set for hydrogen-neon.

631GST

This gets a 6-31G* basis set for hydrogen-argon.

631PGS

This gets a 6-31+G* basis set for hydrogen-argon.

6311PPGSS

This gets a 6-311++G** basis set for hydrogen-neon.

PLUSS

This gets a diffuse S (Pople) for hydrogen-argon.

PLUSP

This gets a diffuse P (Pople) for hydrogen-argon.

EXAMPLE

The following input is for the water molecule:

  default: (
    )

  input: (
    basis = dzp
    geometry = ((o   0.0  0.00000000   0.00000000)
                (h   0.0 -1.49495900   0.99859206)
                (h   0.0  1.49495900   0.99859206))
    )

The following input is equivalent to the above example:

  default: (
    )

  input: (
    basis = ( (o dzp)
              (h dzp) )
    geometry = ((oxygen   0.0  0.00000000   0.00000000)
                (hydrogen 0.0 -1.49495900   0.99859206)
                (hydrogen 0.0  1.49495900   0.99859206))
    )

The following is an example of Z-matrix specification

  default: (
    )

  input: (
    basis = ( (oxygen ccpv6z)
              (hydrogen ccpv5z) )
    zmat  = ((x)
             (o  1 1.0)
             (h  2 0.995  1 127.75) 
             (h  2 0.995  1 127.75  3 180.0) 
            )
    )

BASIS SET EXAMPLE

The following lines input could be placed in an input file to redefine the hydrogen DZP basis set. Note that double quotes must be used when a basis set name has special characters in it.

basis: (
  % definition for hydrogen's DZP basis:
  hydrogen:dzp = (
    % inserts hydrogen:dz:
    (get "DZ")
    % uses pbasis.dat for polarization:
    (get "DUNNING_POLARIZATION")
    )
  % definition for hydrogen's DZ basis:
  hydrogen:dz = (
    % inserts hydrogen:"HUZINAGA-DUNNING_(9S/4S)":
    (get "HUZINAGA-DUNNING_(9S/4S)")
    )
  % definition for hydrogen's (9s/4s) basis:
  hydrogen:"HUZINAGA-DUNNING_(9S/4S)" = (
    (S (     19.2406     0.032828)
       (      2.8992     0.231208)
       (      0.6534     0.817238))
    (S (      0.1776     1.0))
    )
  )

FILES SUBSECTION EXAMPLE

The following lines input could be placed in an input file to define an alternate location to look for basis set information. Note that double quotes must be used when a string has special characters in it.

input: (
  basis = (mydzp mydzp mydzp)
  geometry = ((o 0.0  0.00000000   0.00000000)
              (h 0.0 -1.49495900   0.99859206)
              (h 0.0  1.49495900   0.99859206))
    %  I like to keep everything in my chem applications 
    %  sub directory.
    %  Basis set is in 
    %    /home/general/user/chem/my_very_own.basis
  basis_file = "/home/general/user/chem/my_very_own.basis" 
  )

input: (
  basis_file = "/home/general/user/basis/dzp_plus_diff/"
    %  I like to keep everything in it's own directory.
    %  Basis set is in 
    %    /home/general/user/basis/dzp_plus_diff/basis.dat
  basis = dzpdiff
  geometry = ((o 0.0  0.00000000   0.00000000)
              (h 0.0 -1.49495900   0.99859206)
              (h 0.0  1.49495900   0.99859206) )
  )

LAST THINGS

This program has been written by Edward F. Valeev, Dr. Justin T. Fermann, and Timothy J. Van Huis. Authors would like to thank Dr. T. Daniel Crawford and Rollin A. King for help. Any problems should be e-mailed to [email protected].