4.2.29. MBPT2

4.2.29.1. Description

The MBPT2 program of the Molcas program system computes the second order correlation energy and the reference weight for a closed-shell Hartree–Fock reference wave function, based on a Møller–Plesset partitioning of the Hamiltonian and canonical orbitals.

If SEWARD performed a Cholesky decomposition of the two-electron integrals prior to running the MBPT2 program, Cholesky vectors will be employed for computing the second order energy correction. This is done by first transforming the Cholesky vectors to MO basis and subsequently computing the \((ai|bj)\) integrals. These integrals are either computed, stored on disk, and then read back in to memory during the energy evaluation (i.e. mimicking a conventional calculation) or they may be computed on-the-fly. The user may choose either algorithm through the Cholesky-specific options described below.

If SEWARD did not perform a Cholesky decomposition, the transformation of the two-electron integrals in AO basis (\(\mathcal{O}(N^4)\), where \(N\) is the number of basis functions) to the exchange operator matrices \(\mat{K}^{ij}\) in MO basis (\(\mathcal{O}(O^2)\) matrices of size \(V^2\), where \(O\) and \(V\) denote the number of occupied and virtual orbitals, respectively), is either done conventionally, using the two-electron integral file ORDINT, which was generated in a previous step by the SEWARD integral code.

4.2.29.2. Dependencies

The MBPT2 program requires the communications file RUNFILE. It contains specifications processed by SEWARD, the Hartree–Fock canonical orbitals, eigenvalues and energy generated by SCF. For Cholesky-based calculations, all Cholesky related files (see the manual pages for SEWARD) must be available, whereas for conventional (not integral-direct) calculations the two-electron integral file ORDINT is required. Hence, before running MBPT2, a SEWARD and a SCF run have to be performed.

4.2.29.3. Files

4.2.29.3.1. Input files

MBPT2 will use the following input files: ONEINT, ORDINT, RUNFILE. For Cholesky runs: CHVEC, CHORST, CHRED and CHOR2F (for more information see 4.1.1.2).

4.2.29.3.2. Output files

RUNFILE
File for communication of auxiliary information.

4.2.29.4. Input

Below follows a description of the input to MBPT2. The input for each module is preceded by its name like:

&MBPT2

No compulsory keywords are required for MBPT2. The reference statement mentioned above is sufficient for a default MBPT2 run.

4.2.29.4.1. Optional keywords

TITLe
The line following this line is regarded as a title line
PRINt
Specifies the general print level of the calculation. An integer has to be supplied as argument. The default value, 0, is recommended for production calculations.
FREEze
Specifies the total number of frozen occupied orbitals. The lowest-energy occupied orbitals are then automatically identified and frozen. The keyword takes as argument one integer. Incompatible with the FROZen keyword.
FROZen
Specifies the number of frozen occupied orbitals in each of the irreducible representations (irreps) of the subgroup of \(D_{2h}\) in which the system is represented. The counting of the orbitals follows the increasing orbital energy within each irrep, with those orbitals being frozen first that correspond to lowest orbital energies. The keyword takes as argument nIrrep (# of irreps) integers. Incompatible with the FREEze keyword. Default is to freeze non-valence orbitals.
DELEted

Specifies the number of deleted orbitals in each of the irreducible representations (irreps) of the subgroup of \(D_{2h}\) in which the system is represented. The counting of the orbitals follows the decreasing orbital energy within each irrep, with those orbitals being deleted first that correspond to highest orbital energies. The keyword takes as argument nIrrep (# of irreps) integers.

NOTE: Those orbitals, which have been deleted already in the SCF calculation (cf. SPDElete, OVLDelete of the SCF program description) are never seen by the MBPT2 program and hence are not to be deleted again with the present option.

SFROzen
Allows to specify specific orbitals to freeze in each of the irreducible representations (irreps) of the subgroup of \(D_{2h}\) in which the system is represented. In the 1st line after the keyword the number of orbitals to freeze for each irrep is specified (nIrrep (# of irreps) integers). The next \(\leq\) nIrrep lines reference the orbitals to freeze for the related irrep, following an enumeration of the individual orbitals of 1, 2, 3,… according to increasing orbital energy. Note that the orbital reference numbers obey the original ordering and also include those orbitals which may have been frozen already by the FROZen or FREEze options. If the corresponding irrep does not contain any specific orbitals to freeze (i.e. a zero was supplied for this irrep in the 1st line), no line orbital reference input line is supplied for that irrep.
SDELeted
Allows to specify specific orbitals to delete in each of the irreducible representations (irreps) of the subgroup of \(D_{2h}\) in which the system is represented. In the 1st line after the keyword the number of orbitals to delete for each irrep is specified (nIrrep (# of irreps) integers). The next \(\leq\) nIrrep lines reference the orbitals to delete for the related irrep, following an enumeration of the individual orbitals of 1, 2, 3,… according to increasing orbital energy. Note that the orbital reference numbers obey the original ordering. If the corresponding irrep does not contain any specific orbitals to freeze (i.e. a zero was supplied for this irrep in the 1st line), no line orbital reference input line is supplied for that irrep.
GHOStdelete
Excludes from PT2 treatment orbitals localized on ghost atoms. A threshold for this selection must be specified.
LUMOrb
Molecular orbital coefficients and energies read from INPORB file rather than RunFile.
EREF
Specifies the value of the reference energy. Available only in combination with LumOrb. Default value of the reference energy is set to zero.
TEST
If this keyword is specified the input is checked without performing any calculation.
T1AM
Singles amplitudes/energy introduced according to Thouless formula. An INPORB file containing MOs different from HF orbitals is required.
LOVMp2

“Freeze-and-Delete” type of MP2, available only in connection with Cholesky or RI. An example of input for the keyword LOVM is the following:

LovMP2
2  0.2  (nCenters,thrs)
C1 N    (Center labels)
DoMP2

In this case, both occupied and virtual orbitals (localized by the program) are divided in two groups: those (A) mainly located on the two (symmetry independent) centers C1 and C2, and the remaining ones (B), which are obviously “outside” this region. The value of the threshold (between 0 and 1) is used to perform this selection (in the example, 20% of the gross Mulliken population of a given orbital on the specified atoms). By default, the MP2 calculation is performed only for the correlating orbitals associated with the region A (“active site”). The keyword DoMP2 is optional and forces the program to perform also an independent MP2 calculation on the “frozen region” (B). Alternatively, one can specify the keyword VirAll in order to use all virtual orbitals as correlating space for the occupied orbitals of the active site.

FNOMp2

Performs a Frozen Natural Orbital (FNO) MP2 calculation, available only in combination with Cholesky or RI integral representation. An example of input for the keyword FNOM is the following:

FNOMp2
0.4
DoMP2

The keyword FNOM has one compulsory argument (real number in ]0,1]) specifying the fraction of virtual orbitals (in each irrep) to be retained in the FNO-MP2 calculation. The keyword DoMP2 is optional and used to compute the (estimated) correction for the truncation error.

PRPT
Multipole moments (dipoles and quadrupoles) are calculated and printed. The moments are calculated by using a variational one-particle MP2 density matrix. The calculation of the density matrix substantially increases the computational effort compared to an ordinary energy calculation. If the call to MBPT2 is followed by a LOPROP call the variational MP2 density matrix will automatically be passed on to that module when this keyword is active.
GRDT
Variational one and two-particle MP2 densities are calculated to prepare for analytical gradient calculations. The default for subsequent gradient calculations are changed from numerical to analytical when this keyword is invoked. When using MBPT2 in a SLAPAF-loop with only \(C_1\) symmetry analytical gradients are automatically default and this keyword is not needed. grdt prints Multipole moments and prepare for LOPROP in the exact same way as prpt. Use of this keyword therefore makes it redundant (but harmless) to also specify the keyword prpt.
NOGRdt
Disables the calculation of variational densities for analytical gradients. This is useful to cancel the implicit grdt added when using MBPT2 inside a SLAPAF-loop, if no analytical gradients are actually needed. Note that using the Numerical keyword in GATEWAY already disables grdt, so nogrdt is only needed in some advanced situations.

4.2.29.4.2. Optional keywords specific to Cholesky calculations

Observe that these keywords are disregarded if the integrals were not Cholesky decomposed by SEWARD. Furthermore, they are disregarded for algorithm 0 (see below).

CHOAlgorithm
Takes as argument one positive integer specifying the algorithm to use for Cholesky MP2. Options: 0 [generate MO integrals on disk from Cholesky vectors], 1 [compute integrals on-the-fly, minimal operation count, level 2 BLAS], 2 [compute integrals on-the-fly, not minimal operation count, level 3 BLAS], Default is 2.
VERBose
Increases printing from the Cholesky MP2 routines, although not by much. Default is (almost) no printing.
DECOmpose
Requests Cholesky decomposition of the \((ai|bj)\) integrals. Unless user-defined (see below), the threshold used is identical to that used by SEWARD for decomposing the two-electron integrals. Default is to not decompose.
THRCholesky
Specifies the threshold for \((ai|bj)\) Cholesky decomposition. Takes as argument one real number. Default is the threshold used by SEWARD for decomposing the two-electron integrals.
NODEcompose
Turns off Cholesky decomposition of the \((ai|bj)\) integrals. Default is to not decompose.
SPAN
Specifies the span factor used for \((ai|bj)\) Cholesky decomposition. Takes as argument one real number. Default is the span factor used by SEWARD for decomposing the two-electron integrals.
MXQUal
Specifies the max. number of qualified diagonals treated during \((ai|bj)\) Cholesky decomposition. Takes as argument one integer. Default is 10% of the max. rank of \((ai|bj)\), although never more than 200.
PRESort
Presort the MO Cholesky vectors according to the batches over occupied orbitals. This will reduce the amount of I/O performed during on-the-fly assembly of the \((ai|bj)\) integrals. This keyword is obsolete.

4.2.29.4.3. Limitations

The maximum number of selectively frozen SFRO or selectively deleted orbitals SDEL in each symmetry is limited to 50.

The limitations on the number of basis functions are the same as specified for SEWARD.

4.2.29.4.4. Input example

&MBPT2
Title
 H2O:  O(9.5/4.2), H(4/2)
* The lowest energy occupied orbital in the repr. no.1 will be frozen in
* MBPT2 calculations. The number of representations is 4 and all zeros
* must be explicitly given
Frozen
1 0 0 0
* Two highest energy external orbitals in the repr. no.3 will be deleted
* in MBPT2 calculations. The number of representations is 4 and all
* zeros must be explicitly given
Deleted
0 0 2 0
* One occupied orbital in symmetry no.1 will be additionally frozen by
* using the SFRO option. Let it be the third SCF occupied orbital in
* this symmetry
sFrozen
1 0 0 0   // Gives the number of frozen orbitals in each symmetry
3         // Gives the frozen orbital reference number in symmetry no. 1
* Two external orbitals in symmetry no.1 and one external orbital in
* symmetry 3 will be deleted. In symmetry 1 let it be the second and
* third external orbitals, and in symmetry 3 the third (already deleted
* in by using the option DELE) external orbital
sDeleted
2 0 1 0   // Gives the number of orbitals to be deleted in each symmetry
2 3       // Gives the reference numbers of external orbitals in sym. 1
3         // Gives the reference number of the external orb. in sym. 3