Ubuntu Manpage: detci - Determinant Configuration Interaction Program

NAME

       detci - Determinant Configuration Interaction Program

DESCRIPTION

       The  program  detci diagonalizes the nonrelativistic electronic Hamiltonian operator in a basis of Slater
       determinants.  The set of determinants used (CI space) may be chosen in a variety of ways.   The  program
       can  handle  any  CI  space which can be formulated as a Restricted Active Space CI.  This includes CISD,
       CISDT, CISDTQ, etc., up to Full CI, as well as multireference CI's in which the references are chosen  as
       all  determinants in which up to n electrons are excited in some MO active space.  This includes CISD[T],
       CISD[TQ], and second-order CI (SOCI).

REFERENCES

       Restricted Active Space CI:

       1.     Determinant Based Configuration Interaction Algorithms for Complete and  Restricted  Configuration
              Interaction  Spaces,  J. Olsen, B. O. Roos, P. Jorgensen, and H. J. Aa. Jensen, J. Chem. Phys. 89,
              2185 (1988).

       2.     Passing the One-Billion Limit in Full Configuration-Interaction (FCI) Calculations, J.  Olsen,  P.
              Jorgensen, and J. Simons, Chem. Phys. Lett. 169, 463 (1990).

       Tertiary virtual subspaces (RAS IV):

       1.     Compact  Variational  Wavefunctions  Incorporating Limited Triple and Quadruple Excitations, C. D.
              Sherrill and H. F. Schaefer, J. Phys. Chem. 100, 6069-6075 (1996).

       DETCI Program:

       1.     C. D. Sherrill, Computational Algorithms for Large-Scale Full  and  Multi-Reference  Configuration
              Interaction Wavefunctions, PhD thesis, University of Georgia, Athens, GA, 1996.

FILES REQUIRED

           input.dat          - Input file
           file71             - Transformed one-electron integrals
           file72             - Transformed two-electron integrals

TEMPORARY FILES USED

           file50             - Diagonal of Hamiltonian
           file51             - CI vectors
           file52             - Sigma vectors
           file53             - D file (correction vectors)

FILES UPDATED

           output.dat         - Output file

INPUT FORMAT

The following command-line arguments are available:

-quiet This gives the same result as PRINT=0.

-o fname
Gives the filename for the output file. Defaults to output.dat.

-e This option causes the total CI energy or energies to be written to a file called
detci_energies.dat.

-c value
Gives a looser convergence on the CI vector, useful in DETCAS calculations. The value is a real
number, not an integer as in CONVERGENCE. The convergence used will be the looser of value and
CONVERGENCE.

Additional input for this program is read from the file The following keywords are valid:

CONVERGENCE = integer
Convergence desired on the CI vector. Convergence is achieved when the RMS of the error in the CI
vector is less than 10**(-n). The default is 4 for energies and 7 for gradients. This is not the
same CI vector convergence criterion as found in GUGACI.

DOCC = integer_array
This vector gives the number of doubly occupied orbitals in each irrep. There is no default.

SOCC = integer_array
This vector gives the number of singly occupied orbitals in each irrep. There is no default.

DIAG_METHOD = string
This specifies which method is to be used in diagonalizing the Hamiltonian. The valid options
are: RSP, to form the entire H matrix and diagonalize using libciomr to obtain all eigenvalues
(n.b. requires HUGE memory); OLSEN, to use Olsen's preconditioned inverse subspace method (1990);
MITRUSHENKOV, to use a 2x2 Olsen/Davidson method; and DAVIDSON (or SEM) to use Liu's Simultaneous
Expansion Method, which is identical to the Davidson method if only one root is to be found.
There also exists a SEM debugging mode, SEMTEST. The SEM method is the most robust, but it also
requires 2(N*M)+1 CI vectors on disk, where N is the maximum number of iterations and M is the
number of roots.

PRECONDITIONER = string
This specifies the type of preconditioner to use in the selected diagonalization method. The
valid options are: DAVIDSON which approximates the Hamiltonian matrix by the diagonal elements;
H0BLOCK_INV which uses an exact Hamiltonian of H0_BLOCKSIZE and explicitly inverts it;
GEN_DAVIDSON which does a spectral decomposition of H0BLOCK; ITER_INV using an iterative approach
to obtain the correction vector of H0BLOCK. The H0BLOCK_INV, GEN_DAVIDSON, and ITER_INV
approaches are all formally equivalent but the ITER_INV is less computationally expensive.
Default is DAVIDSON.

REFERENCE = string
This specifies the type of reference function. This is RHF or ROHF. UHF and TWOCON are not
supported. For ROHF, a multiplicity of 1 implies an open-shell singlet. The program will run for
open-shell singlets, but it has not been properly adapted to use a correct two-determinant
reference in this case, so running with open-shell singlet references is not advised except for
full CI's.

UPDATE = string
DAVIDSON employs the standard DAVIDSON update or correction vector formula, while OLSEN uses the
OLSEN correction vector. Default is DAVIDSON.

HD_OTF = boolean
If TRUE the diagonal elements of the Hamiltonian matrix are computed on-the-fly, otherwise a
diagonal element vector is written to a separate file on disk. Default is TRUE.

HD_AVE = string
HD_EXACT uses the exact diagonal energies which results in expansion vectors which break spin
symmetry. HD_KAVE averages the diagonal energies over a spin-coupling set yielding spin pure
expansion vectors. ORB_ENER employs the sum of orbital energy approximation giving spin pure
expansion vectors but usually doubles the number of davidson iterations. EVANGELISTI uses the sums
and differences of orbital energies with the SCF reference energy to produce spin pure expansion
vectors. LEININGER approximation which subtracts the one-electron contribution from the orbital
energies, multiplies by 0.5, and adds the one-electron contribution back in, producing spin pure
expansion vectors and developed by yours truly and works as well as EVANGELISTI.

NODFILE = boolean
Only possible if NUM_ROOTS = 1. Uses the last vector space in the BVEC file to write scratch DVEC
rather than using a separate DVEC file.

ENERGY_CONVERGENCE = integer
Convergence desired on the CI energy. The default is 6 for single point energies and 8 for
gradients or CASSCF.

EX_LVL = integer
Excitation level for excitations into virtual orbitals (default 2, i.e. CISD).

VAL_EX_LVL = integer
Excitation level for references in orbitals of RAS II. Defaults to zero.

FCI = boolean
If this flag is set to TRUE, then the storage of strings is simplified for a Full CI and the
calculation requires less overhead. However, the final results should be identical to those when
FCI = FALSE. May cause unpredictable results if FCI = TRUE but EX_LVL is not consistent with a
Full CI.

FROZEN_DOCC = integer_array
The number of lowest energy doubly occupied orbitals in each irreducible representation from which
there will be no excitations. The Cotton ordering of the irredicible representations is used.
The default is the zero vector.

FROZEN_UOCC = integer_vector
The number of highest energy unoccupied orbitals in each irreducible representation into which
there will be no excitations. The default is the zero vector.

FREEZE_CORE = boolean
This option determines whether the frozen core orbitals are to be included implicitly (true) or
explicitly (false). In the former case, the energetic contributions from the frozen core orbitals
are folded into the one-electron integrals and into the "frozen core energy" computed by the
transformation program. The default is true.

EXPORT_VECTOR = boolean
This specifies whether to store converged vector(s) at the end of the run. The vector(s) is(are)
stored in a transparent format such that other programs can use it easily. The format is specified
in src/lib/libqt/slaterdset.h. The default is false.

NUM_EXPORT = integer
If EXPORT_VECTOR is set to true, the this determines the number of vectors that need to be
exported at the end of the run. The default is 1.

GUESS_VECTOR = string
This specifies which type of guess vector to use in the CI iteration. Currently only used by the
SEM iteration method. Accepted values are UNIT for a unit vector guess (NUM_ROOTS and
NUM_INIT_VECS must both be 1); H0_BLOCK to use eigenvectors from the H0 BLOCK submatrix (default);
DFILE to use NUM_ROOTS previously converged vectors in the D file; and MP2 to use the MP2
wavefunction as a guess (not working at the moment).

H0_BLOCKSIZE = integer
This parameter specifies the size of the "H0" block of the Hamiltonian which is solved exactly.
The n determinants with the lowest SCF energy are selected, and a submatrix of the Hamiltonian is
formed using these determinants. This submatrix is used to accelerate convergence of the CI
iterations in the OLSEN and MITRUSHENKOV iteration schemes, and also to find a good starting guess
for the SEM method if GUESS_VECTOR = H0_BLOCK. Defaults to 40. Note that the program may change
the given size for Ms=0 cases (Ms0 = TRUE) if it determines that the H0 block includes only one
member of a pair of determinants related by time reversal symmetry. For very small block sizes,
this could conceivably eliminate the entire H0 block; the program should print warnings if this
occurs.

H0_BLOCK_COUPLING_SIZE = integer
Parameters which specifies the size of the coupling block within the generalized davidson
preconditioner. Default value is 1000.

MAX_DET = integer
Sets the maximum number of determinants; if the CI space is larger than this, the program aborts.
This option exists to ensure that very large calculations are not run by accident. During the
current developmental phase, the default is 10000, but it will be raised before long.

MAXITER = integer
Maximum number of iterations to diagonalize the Hamiltonian. Defaults to 12.

Ms0 = boolean
If TRUE, use the Ms=0 component of the state. Defaults to TRUE if closed-shell and to FALSE
otherwise. Related to the S parameter.

NPRINT = integer
This value specifies the number of determinants which will be printed, along with their
coefficients, in the list of most important determinants in the final CI vector. The default is
20.

NUM_ROOTS = integer
This value gives the number of roots which are to be obtained from the secular equations. The
default is one. If more than one root is required, set DIAG_METHOD to SEM (or, for very small
cases, RSP or SEMTEST).

NUM_INIT_VECS = integer
The number of initial vectors to use in the CI iterative procedure. Defaults to the number of
roots.

OPDM = boolean
If TRUE calculate the one-particle density matrix and make OPDM_WRITE default to TRUE. The
default value of OPDM is FALSE.

OPDM_FILE = integer
File (unit number) for writing the one-particle density matrix if OPDM_WRITE = TRUE. The default
value is currently 73.

OPDM_WRITE = boolean
Flag for whether or not to write the one-particle density matrix to disk.

OPDM_PRINT = boolean
Flag for whether or not to print the one-particle density matrix.

OPDM_DIAG = boolean
Flag for whether or not to diagonalize the one-particle density matrix.

WRTNOS = boolean
Flag for whether or not to write the CI natural orbitals to PSIF_CHKPT.

ORBSFILE = integer
File (unit number) for writing various CI natural orbitals. The default value is 76.

OPDM_AVE = boolean
Flag for whether or not to average the OPDM over several roots in order to obtain a state-average
one-particle density matrix. This density matrix can be diagonalized to obtain the CI natural
orbitals.

ORBS_ROOT = integer
Flag for setting the root number for which CI natural orbitals are written to PSIF_CHKPT. The
default value is 1 (lowest root).

PRINT = integer
This option determines the verbosity of the output. A value of 1 or 2 specifies minimal printing,
a value of 3 specifies verbose printing. Values of 4 or 5 are used for debugging. Do not use
level 5 unless the test case is very small (e.g. STO H2O CISD).

ROOT = integer
The root to write out the two-particle density matrix for (the one-particle density matrices are
written for all roots). Useful for a state-specific CASSCF or CI optimization on an excited
state.

S = integer
The value of the spin quantum number S is given by this option. The default is 0 (singlet). The
only thing this is actually used for is determining the phase of the redundant half of the CI
vector when the Ms=0 component is used (i.e., Ms0 = TRUE). For cases where S is not an integer,
this parameter need not be entered because such a state can't have an Ms=0 component.

TPDM = boolean
If TRUE calculate the two-particle density matrix and make TPDM_WRITE default to TRUE. The
default value of TPDM is FALSE.

TPDM_FILE = integer
File (unit number) for writing the two-particle density matrix if TPDM_WRITE = TRUE. The default
value is currently 74.

TPDM_WRITE = boolean
Flag for whether or not to write the two-particle density matrix to disk.

TPDM_PRINT = boolean
Flag for whether or not to print the two-particle density matrix. Typically a very bad idea
except for debugging small cases.

There is also some less commonly used input, which novice uses of PSI will have no need to use.

BENDAZZOLI = boolean
Use some routines to calculate sigma based on the papers of Bendazzoli et al. Seems to be slower
and not worthwhile; may disappear eventually. Works only for full CI and I don't remember if I
could see how their clever scheme might be extended to RAS in general.

CALC_SSQ = boolean
If TRUE, calculate the expectation value of the S^2 operator for the final CI wavefunction for
each root. In principle, DETCI should yield S^2 eigenfunctions. The default is FALSE.

COLLAPSE_SIZE integer
Gives the number of vectors to retain when the Davidson subspace is collapsed (see MAXNVECT
below). If greater than one, the collapsed subspace retains the best estimate of the CI vector
for the previous n iterations. Defaults to 1.

FIRST_TMP_UNIT = integer
Gives the file (unit) number associated with the first scratch file used by DETCI. Other scratch
files are numbered consecutively from this point, int the order H(diag), C, S, D. Each of these
logical files takes up a number of physical files specified by the even more obscure input
parameters NUM_HD_TMP_UNITS, NUM_C_TMP_UNITS, NUM_S_TMP_UNITS, NUM_D_TMP_UNITS. The user can also
specify different starting points for each of these sets using the parameters FIRST_HD_TMP_UNIT
and so forth. Splitting a file across several units may help avoid the size-of-integer problem in
addressing large files that is present in DETCI and in PSI I/O libraries; but then again, I
haven't tested it to see what happens. The first unit of each section is printed out under the
heading FILES in the parameter output beginning the DETCI run.

FZC = boolean
Determines whether the frozen core orbitals are treated as truly frozen (i.e., absent entirely
from calculation, FZC = TRUE) or whether they are present but restricted to be doubly occupied
(FZC = FALSE). In the GUGA CI program, this is the distinction between what it calls FZC and COR
orbitals. Generally, the integrals for frozen core orbitals are not needed by DETCI but they may
be needed for MCSCF or gradients.

ICORE = integer
Specifies how to handle buffering of CI vectors. A value of 0 makes the program perform I/O one
RAS subblock at a time; 1 uses entire CI vectors at a time; and 2 uses one irrep block at a time.
Values of 0 or 2 cause some inefficiency in the I/O (requiring multiple reads of the C vector when
constructing H in the iterative subspace if DIAG_METHOD = SEM), but require less core memory.

ISTOP = boolean
If TRUE then DETCI will stop after string information is formed and before integrals are read.
May eventually change to an integer so that the user can select from multiple stopping points.

MAXNVECT = integer
Gives the maximum number of Davidson subspace vectors which can be held on disk for the CI
coefficient and sigma vectors. (There is one H(diag) vector and the number of D vectors is equal
to the number of roots). When the number of vectors on disk reaches the value of MAXNVECT, the
Davidson subspace will be collapsed to COLLAPSE_SIZE vectors for each root. This is very helpful
for saving disk space. Defaults to MAXITER * NUM_ROOTS + NUM_INIT_VECS.

MIXED = boolean
This determines whether "mixed" RAS II/RAS III excitations are allowed into the CI space. This is
useful for placing additional constraints on a RAS CI.

MIXED4 = boolean
This is similar to the MIXED keyword, but refers to excitations into RAS IV.

NUNITS = integer
Number of scratch files to be used in storing the C vectors (and also for the sigma vectors).

OEI_ERASE = boolean
This determines whether the program erases the one-electron integrals file after it has been read.
The default will eventually be true, but during development the default is false.

OEI_FILE = integer
This keyword allows the user to specify the transformed one-electron integral file. The default
is 71.

PRINT_CIBLKS = boolean
Specifies whether the program should print out a summary of all the blocks in the CI vector (which
can be cast into matrix form, see refs.)

R4S = boolean
Restricts the RAS IV strings to the minimal set, saving memory. If you are concerned about this
option, you should write David for advice unless you are a DETCI expert.

REF_SYM = integer
This option allows the user to look for CI vectors of a different irrep than the reference. This
probably only makes sense for Full CI, and it would probably not work with unit vector guesses.
Numbering starts from zero for the totally-symmetric irrep.

REPL_OTF = boolean
Tells DETCI whether or not to do string replacements on the fly. Can save a gigantic amount of
memory (especially for truncated CI's) but is somewhat flaky and hasn't been tested for a while.
As I recall, it only works for certain classes of RAS calculations. Contact David for assistance.
Eventually, the on-the-fly replacement stuff should be redone in a much smarter way so that it
doesn't take eons of CPU time. Work along these lines was once started and may be completed
eventually.

RESTART = boolean
This option allows the user to resume a DETCI iteration that terminated prematurely. It assumes
that the CI and sigma vectors are on disk; the number of vectors specified by RESTART_VECS is
collapsed down to one vector per root.

RESTART_VECS = integer
If RESTART = TRUE this specifies the number of CI (and sigma) vectors to read from disk.
Typically this is the number of successfully completed iterations from a previous run times the
number of roots for that run.

TEI_ERASE = boolean
This determines whether the program erases the two-electron integrals file after it has been read.
The default will eventually be true, but during development the default is false.

TEI_FILE = integer
This keyword allows the user to specify the transformed two-electron integral file. The default
is 72.

MPN = boolean
When this option is TRUE DETCI will compute the MPn series out to kth order where k is determined
by maxnvect. For open-shell systems (REF=ROHF, WFN = ZAPTN), DETCI will compute the ZAPTn series.
GUESS_VECTOR must be set to TRUE. HD_OTF must be set to TRUE. HD_AVE must be set to orb_ener.

SAVE_MPN2 = integer
When MPN is TRUE and WIGNER is TRUE then this option becomes valid. If set to 1 then MP(2n-1)
energy is saved. If set to 2 then MP(2n-2) energy is saved. If any other value MPn energy is
saved. The default is 0.

9 Feb, 1996 detci(1)