*Code author: C. David Sherrill and Matthew L. Leininger*

*Section author: C. David Sherrill*

*Module:* *Keywords*, *PSI Variables*, DETCI

Configuration interaction (CI) is one of the most general ways to improve upon Hartree–Fock theory by adding a description of the correlated motions of electrons. Simply put, a CI wavefunction is a linear combination of Slater determinants (or spin-adapted configuration state functions), with the linear coefficients being determined variationally via diagonalization of the Hamiltonian in the given subspace of determinants. For a “single-reference” CI based on reference function , we can write the CI expansion as follows:

(1)

The simplest standard CI method that improves upon Hartree–Fock is a CI that adds all singly and doubly substituted determinants (CISD) to the reference determinant . The CISD wavefunction has fallen out of favor because truncated CI wavefunctions are not size-extensive, meaning that their quality degrades for larger molecules. MP2 is a less expensive alternative giving results similar to those of CISD for small molecules, but the quality of MP2 does not degrade for larger molecules. Coupled-cluster singles and doubles (CCSD) is another size-extensive alternative; it is only slightly more costly computationally than CISD, but it typically provides significantly more accurate results.

The CI code in PSI4 is described in detail in [Sherrill:1999:CI]. For the reasons stated above, the CI code in PSI4 is not optimized for CISD computations. Instead, emphasis has been placed on developing a very efficient program to handle more general CI wavefunctions which may be helpful in more challenging cases such as highly strained molecules or bond breaking reactions. The CI code is based on the fast, determinant-based string formalism of Handy [Handy:1980]. It can solve for restricted active space configuration interaction (RAS CI) wavefunctions as described by Olsen, Roos, Jorgensen, and Aa. Jensen [Olsen:1988]. Excitation-class selected multi-reference CI wavefunctions, such as second-order CI, can be formulated as RAS CI’s. A RAS CI selects determinants for the model space as those which have no more than holes in the lowest set of orbitals (called RAS I) and no more than electrons in the highest set of orbitals (called RAS III). An intermediate set of orbitals, if present (RAS II), has no restrictions placed upon it. All determinants satisfying these rules are included in the CI.

The DETCI module is also very efficient at computing full configuration interaction wavefunctions, and it is used in this capacity in the complete-active-space self-consistent-field (CASSCF) code. Use of DETCI for CASSCF wavefunctions is described in another section of this manual.

As just mentioned, the DETCI module is designed for challenging
chemical systems for which simple CISD is not suitable. Because
CI wavefunctions which go beyond CISD (such as RAS CI) are fairly complex,
typically the DETCI code will be used in cases where the
tradeoffs between computational expense and completeness of the
model space are nontrivial. Hence, the user is advised to develop
a good working knowledge of multi-reference and RAS CI methods before
attempting to use the program for a production-level project. This user’s
manual will provide only an elementary introduction to the most
important keywords. Additional information is available in the complete
list of keywords for DETCI provided in Appendix *DETCI*.

The division of the molecular orbitals into various subspaces such as
RAS spaces, or frozen *vs.* active orbitals, *etc.*, needs to be clear not
only to detci, but also at least to the transformation program
(and in the case of MCSCF, to other programs as well). Thus, orbital
subspace keywords such as *RAS1*,
*RAS2*, *RAS3*, *FROZEN_DOCC*, *FROZEN_UOCC*,
*ACTIVE*, etc., should be set
in the global section of input so they may also be read by other modules.

For single-reference CI computations, the easiest way to invoke a CI
computation with DETCI is simply to call `energy()`, `optimize()`, etc.,
with the common name for that CI wavefunction, like `energy('cisd')`
for a CISD single-point energy. The Python driver
recognizes `cisd`, `cisdt`, and `cisdtq`. Higher order
single-refernce CI wavefunctions, like those including singles through
6-fold excitations, can be invoked using numbers, like `ci6`. A full
CI can be specifed by `fci`. More complicated CI computations, like
RASCI, can be performed by setting the appropriate keywords and calling the
module generically like `energy('detci')`. The latter approach
will also work for any of the previously-mentioned CI wavefunctions for
which the driver has built-in shortcuts, so long as the relevant options
(especially *EX_LEVEL*) are set appropriately. Some
examples of single-refence CI, RASCI, and full CI computations are provided
in psi4/samples.

Convergence criterion for CI residual vector in the Davidson algorithm (RMS error). The default is 1e-4 for energies and 1e-7 for gradients.

Type:conv doubleDefault: 1e-4

An array containing the number of frozen doubly-occupied orbitals per irrep (these are not excited in a correlated wavefunction, nor can they be optimized in MCSCF

Type: arrayDefault: No Default

An array containing the number of frozen unoccupied orbitals per irrep (these are not populated in a correlated wavefunction, nor can they be optimized in MCSCF

Type: arrayDefault: No Default

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.

Type: integerDefault: 1

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; andDAVIDSON(orSEM) 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. TheSEMmethod is the most robust, but it also requires CI vectors on disk, where is the maximum number of iterations and is the number of roots.

Type: stringPossible Values: RSP, OLSEN, MITRUSHENKOV, DAVIDSON, SEM, SEMTESTDefault: SEM

Do compute one-particle density matrix if not otherwise required?

Type:booleanDefault: false

Do compute the transition density? Note: only transition densities between roots of the same symmetry will be evaluated. DETCI does not compute states of different irreps within the same computation; to do this, lower the symmetry of the computation.

Type:booleanDefault: false

Do compute the MPn series out to kth order where k is determined by

MAX_NUM_VECS? For open-shell systemsREFERENCEis ROHF,WFNis ZAPTN), DETCI will compute the ZAPTn series.GUESS_VECTORmust be set to UNIT,HD_OTFmust be set to TRUE, andHD_AVGmust be set to orb_ener; these should happen by default for MPN = TRUE.

Type:booleanDefault: false

For larger computations, additional keywords may be required, as
described in the DETCI section of the Appendix *DETCI*.

The DETCI module is capable of computing energies for arbitrary order Møller–Plesset perturbation theory (MPn, for closed-shell systems with an RHF reference) and for Z-averaged perturbation theory (ZAPTn, open-shell systems with an ROHF reference). However, please note that these computations are essentially doing high-order CI (up to full CI) computations to obtain these results, and hence they will only be possible for very small systems (generally a dozen electrons or less).

The simplest way to run high-order perturbation theory computations is to
call, *e.g.*, `energy('mp10')` to invoke a MP10 computation or
`energy('zapt25')` to invoke a ZAPT25 computation. This will
automatically set several additional user options to their appropriate
values. The program uses the Wigner (2n+1) rule to obtain higher-order
energies from lower-order wavefunctions.

For the interested reader, the additional user options that are
automatically set up by the calls above are as follows. A call like
`energy('mp10')` sets *MPN* to TRUE.
The program uses the Wigner (2n+1) rule by default
(*MPN_WIGNER* = TRUE)
and figures out what order of wavefunction is
necessary to reach the desired order in the energy. The program then
sets *MAX_NUM_VECS* to the required order in the
wavefunction.
By default, the requested n-th order energy is saved as the current
energy to the process environment. ZAPTN works essentially the same
way for an ROHF reference.

*This DETCI-based version of this feature is not yet released. However,
the current version of the code does include an interface to*
*Kallay’s MRCC* *code.*

The DETCI module is also capable of computing arbitrary-order
coupled-cluster energies, using an approach similar to that of Hirata
and Bartlett [Hirata:2000:216], or of Olsen [Olsen:2000:7140].
Notably, the approach in DETCI also allows arbitrary-order
*active space* coupled-cluster procedures. The general algorithm
for doing this in DETCI is inefficient compared to optimized
lower-order coupled-cluster codes and should not be used for CCSD,
where the CCENERGY module is much more efficient. For higher-order
CC (like CCSDT and beyond), the code is also not as efficient as the
MRCC code by Kállay, to which PSI4 can interface (see Section
*Interface to MRCC by M. Kállay*); however, it may allow certain truncations of the model
space that might not be available presently in MRCC. For very small
systems, the code can be useful for testing of, for example, CCSDTQ or
its active-space CCSDtq analog [Piecuch:1999:6103].

To perform arbitrary-order coupled-cluster, set the DETCI
option *CC* to TRUE, and set
*CC_EX_LEVEL* (note: not *EX_LEVEL*)
to the desired coupled-cluster excitation level, and invoke
`energy('detci')`. Various other DETCI options have a similar
option for coupled-cluster, usually named beginning with CC. The full
list of options is given in Appendix *DETCI*.