# Overlay 10

IOp(10/5)

Calculation of first derivatives of post-SCF energies. Only implemented for closed-shell and UHF.

0 | No. |

1 | Calc. D E(MP2) / D R |

2 | Calc. D E(CID) / D R |

3 | Calc. D E(CISD) / D R |

4 | Calc. D E(CIS/TD) / D R |

5 | Calc. D E(CCD) / D R |

6 | Calc. D E(CCSD/QCISD) / D R |

7 | Calc. D E(BD) / D R |

8 | Calc. D E(MP3) / D R |

9 | Calc. D E(MP4) /D R |

00 | Default CPHF usage (Z-vector unless HF D2E). |

10 | Full 3*NAtoms CPHF. |

20 | Z-Vector method. |

30 | Test Z-Vector using full CPHF. |

000 | Default derivative processing — just set up here unless doing HF 2nd derivatives simultaneously. |

100 | Compute F1 and S1 derivative terms here. |

200 | Don’t process any derivative terms here. Setup for external processing of W and Z. |

0xxx | Default (1). |

1xxx | Compute forces. |

2xxx | Do nonadiabatic coupling in addition to forces, skipping CPHF. Only implemented for TD. |

3xxx | Do nonadiabatic coupling in addition to forces, doing CPHF. Only implemented for CIS and TD. |

4xxx | Do nonadiabatic coupling instead of forces, skipping CPHF. Only implemented for TD. |

5xxx | Do nonadiabatic coupling instead of forces, doing CPHF. Only implemented for CIS and TD. |

IOp(10/6)

Calculation of the second derivatives of the SCF energy. Available for RHF and UHF only. Partially coded but NYI for high-spin ROHF.

0 | No. |

1 | Yes, do D2 E(SCF) / D R(I) D R(J). |

2 | Setup for MP2 2nd derivatives (i.e. No contributions to the force constants are done here). |

3 | Same as 1, but do not do any 3rd order properties. |

4 | Same as 0 if doing post-SCF gradients or same as 2 otherwise. This makes possible to run L1014 with in the old way, i.e. using IRwP1 and IRwW1. |

00 | Default: use new Px/Wx digestion code if possible, save as little data as possible. |

10 | Use old Px/Wx digestion code. |

20 | Use new Px/Wx code but save both S1 and F1 over MOs. |

30 | Use new Px/Wx code and don’t save S1 but do save F1. |

100 | Compute dipole derivatives using only electric field CPHF and F(x) matrices. |

200 | Compute dipole-dipole, dipole-quadrupole, and OR tensors. |

300 | Combination of 100 and 200 |

1000 | Set up for GIAO MP2 calculation. |

10000 | Do DFT 3rd derivatives. |

20000 | Do hyperpolarizabilities for second-harmonic generation. |

000000 | Default (don’t do magnetic susceptibility). |

100000 | Do magnetic susceptibility. |

200000 | Don’t do magnetic susceptibility. |

IOp(10/7)

RMS convergence on C1(I,A) contributions. The max element is tested against 10* this value.

0 | Default: 1.D-8, except 1.D-10 for Z-Vector CPHF or SSC including Fermi Contact. |

N | 1.D-N. |

L1003: Accuracy of CPMCSCF convergence. Only used for Direct CPMCSCF. Convergence = 10^{-K}. For default value, see IOp(50).

IOp(10/8)

Selection of linear equation solution method.

0 | Default (same as 2, except for ZDO non-ONIOM-EE). |

-1 | Solve CPHF for each variable in a separate call to LinEq1. |

1 | Expand each variable in a separate expansion space. This is the default and necessary for frequency-dependent perturbations at multiple frequencies, and is the default if there is only 1 perturbation or if the convergence is set to less 10.d-10. |

2 | Solve all equations together, possibly reverting to the old (one variable at a time) method in the secondary solution. This is the default for multiple perturbations at the same or zero frequency with the default convergence. |

3 | Invert the A matrix directly. |

0x | Default: 2 if memory permits, or 3 if the number of right-hand sides is significantly larger than N0 (the number after orthogonalization). If memory does not permit direct solution, then 4 if there is sufficient memory to form the inverse and the reduced dimension is still below that specified by IOp(11), or 1 if all others are rejected. |

1x | Use recursive DIIS with simultaneous solution. |

2x | Solve linear equations for all N RHS in reduced space. |

3x | Solve linear equations for N0 RHS in reduced space. |

4x | Invert the reduced A-matrix. |

0xx | Default NormTp in LinEq2 (3, except for 2nd order CPHF for Raman/ROA, where it depends on IOp(92)). |

1xx | Full normalization |

2xx | Normalize input vectors with norm > 1. |

3xx | No normalization. |

IOp(10/10)

Control of CPMCSCF during avoided crossing/conical intersection searches.

L1003: The most useful options for IOp(10) are as follows (assumes L510 is run with IOp(14)=310000 or 300000):

600006 | Optimize lowest energy point on a conical intersection (or n-1)hyperline IOp(10)=600006. This takes one state to be IOp(28) and the other IOp(28)-1. |

600005 | As for IOp(10)=600006 but solves CP-MCSCF equation. Usually a very small correction but you must check. Needs IOp(17)=200 in l510 (Orbital Hessian). |

300006 or 300005 | Optimize (e2-e1)^{2}. Not meaningful alone; can be used to start a diff. crossing search. |

700007 | Computes the SA-CPMCSCF corrected gradient for the Ivec state, and writes it for use in other links. Also computes the SA second derivatives. (The only approximation is the neglect of the second order orbital rotation derivatives.) |

700006 | Computes the SA-CPMCSCF corrected gradient for the Ivec state, and writes it for use in other links. |

000 00X | Extras at CP-MCSCF, where X=: |

1: Non-optimum orbitals (obsolete). | |

2: Non-optimum vector (obsolete). | |

3: Non-optimum orbitals without Z-vector trick (obsolete). | |

4: Calculate Ha contribution to Der Cp via <Ci|H|Cj> disactivated. | |

5: Conical intersection information. | |

6: Conical intersection information without solving CP equations (approx. values). | |

7: Compute approximation of the SA second derivatives. | |

8: Conical intersection information using Z-vector trick. This option should be set if solving the cpmcscf equations for either a SA gradient or conical intersection optimization only compatible with IOp(50=2 or 3 or with Hessian inversion IOp(17=0). | |

000 QL0 | Reserved for future use. |

00N 000 | Other state in grdiff/dercpl. |

N: Calculate the derivative couplings of the Nth state. Defaults to IOp(28)-1 so not required. | |

0M0 000 | Contribution to be included at derivative coupling, where M=: |

0: Both CI and orbs are included. DC=Ea+Ex+Ey. | |

1: Only CI contribution. DC= Ea. | |

2: CI and ortho contributions will be included. DC= Ea+Ey. | |

3: Only orbital contribution will be here DC=Ex. | |

4: Orbital and ortho contributions. DC=Ex+Ey. | |

K00 000 | Which gradient to use at the optimization links, where K=: |

0: (Scaled gradient difference or Fxyz). | |

1: Derivative coupling(without division by energy diff.) | |

2: -//- -//- (after -//- -//- -//-) | |

3: Unscaled gradient difference * E2-E1. | |

4: Projection of ivec gradient. | |

5: Read forces from the input stream (test purposes). | |

6: Normalized gradient difference * E2-E1 + projected ivec gradient (conical intersection searches). | |

7: iVec gradient. | |

8: force (n-1) intersection search (to be used if GD is small). |

IOp(10/11)

Largest matrix for direct inversion in LinEq2.

0 | Default (10000). |

-1 | Always use DIIS, never invert directly. |

N | Use DIIS recursively if the O(N^{3}) work (N*N*NSolve) is at least N^{3}. Rounded to an even multiple of 1000. |

IOp(10/13)

The nature of the perturbation(s).

0 | Default (1st order nuclear and electric field). |

IJKL | Nuclear Lth order. Electric field Kth order. Magnetic field Jth order. Nuclear magnetic moment Ith order. |

IOp(10/14)

Whether to update dipole and polarizability derivatives.

0 | Default (yes if IOp(5) = 0). |

1 | Update dipole. |

2 | Don’t update dipole |

10 | Update polarizability. |

20 | Don’t update polarizability. |

100 | Force 2nd order cphf for polarizability derivatives. |

IOp(10/15)

What to do with expansion vectors from the linear equations.

0 | Default (2). |

1 | Save vectors at end. |

2 | Delete vectors at end of each CPHF. |

3 | Pass vectors from 1st to 2nd order CPHF, but delete at end of link (off given defaults in CPHF). |

4 | Save only static electric field solutions. |

00 | Default (use old vectors if available). |

10 | Use old vectors if available. |

20 | Ignore old vectors. |

Note that because of numerical instabilities in the simultaneous solution method, reusing old expansion vectors for new B vectors can reduce accuracy. This may be acceptable in the electric field second-order CPHF, which is used only for one term in polarizability derivatives and for which the accuracy requirements are less stringent, but use of electric field expansion vectors for nuclear coordinate CPHF can cause errors of up to 1 cm^{-1} with current tolerances. This option is normally used to pass 1st order electric field results to the second invocation of 1002 during frequency calculations.

IOp(10/16)

Convergence in secondary linear equations (only for simultaneous solution).

0 | Use standard machine tolerance (MDCutO) on maximum and rms. |

N | Convergence is 10^{-N} for max and rms. |

IOp(10/17)

Frozen-core.

0 | Default (use AO 2PDM for Lagrangian only if orbitals are frozen in /Orb/). |

1 | Do C1, C2, S1, and S2 off the AO 2PDM. |

2 | Convert /Orb/ to full, for debugging frozen-core with integrals over the full window. |

3 | Save as 2, but leave the full version of /Orb/ on the disk. |

L1003: Controls direct or in-core version of CPMCSCF.

000 | In-core version. Must be used with IOp(5/17=200). |

400 | Direct solution of CPMCSCF equations. Must be used with IOp(5/17=400). |

IOp(10/18)

Whether to do correct or approximate CPHF.

0 | CPHF is done correctly. |

1 | The A-matrix is neglected, and hence the U-matrices are set equal to the B-matrices (i.e., uncoupled Hartree-Fock is used). |

2 | The U-matrices are set to zero. |

3 | Only a single set of products AX are computed, independent of convergence criteria. Simultaneous solution is implied. |

IOp(10/19)

Whether overlap (S1) terms must be included.

0 | Default (yes, unless ZDO). |

1 | Yes. |

2 | No. |

Note that the appropriate RWF (588) must be present in any case.

IOp(10/20)

How to handle 2e integral contributions.

0 | Default (decide on the fly). |

1 | Read the 2e integral files, MO if possible. |

2 | Compute the 2e integrals when needed. |

3 | Force use of AO integrals, even if MO ones are available, i.e. force AO or direct. |

4 | Don’t use <IA||BC> integrals, even if present. |

MNx | Use option MN in control of 2e integral calculation. |

IOp(10/21)

Whether to store Uai, Spq, and full MO Fock matrix derivatives in permanent RWFs.

0 | Default (No). |

1 | Yes. Disables use of symmetry to reduce the size of the CPHF problem here. |

2 | No. |

10 | Save magnetic MO derivatives. |

IOp(10/22)

Which multipole (electric field) perturbations to include? Only used if J part of IOp(10/13) is non-zero.

0 | Default. Uniform electric field (dipole) only. |

1 | Dipole (uniform electric field). |

2 | Quadrupole (electric field gradient, all 6 Cartesian components). |

3 | Octupole. |

4 | Hexadecapole. |

IOp(10/28)

State for CPCIS/CPTD, CPMCSCF, and NAC.

0 | Default (1). |

N | Nth excited state. |

IOp(10/29)

Use of Raffenetti integrals during direct SCF.

-N | All integrals done as Raffenetti if there are N or more matrices; all as regular if there are < N. |

0 | Default: let FoFJK decide. |

1 | All integrals are done as regular integrals. |

N | Integrals with degree of contraction greater than or equal to N are done are regular integrals. |

IOp(10/30)

In-core storage of 2e integrals.

0 | Default — do if possible in direct calculation. |

1 | Force in-core storage; recover ints if available on RWF 610. |

2 | Force recomputation. |

IOp(10/31)

Whether to use symmetry to reduce the number of CPHF equations.

0 | Default (yes). |

1 | No. |

2 | Yes. |

3 | Yes, Override check of density matrix symmetry. |

00 | 2e integral symmetry in CPHF (default 2, except 3 for nuclear derivatives). |

10 | No. |

20 | Yes, via petite list if possible, integral replication if not. |

30 | Yes, via integral replication. |

IOp(10/32)

L1014: Whether to apply interchange.

0 | Default (Yes). |

1 | Yes. |

2 | No. |

L1003: Whether to read D2E file.

0 | Default (No). |

1 | Yes. |

2 | No. |

IOp(10/45)

Type of gauge transformations to perform to calculate the current distribution within the molecule, and hence the molecule’s other magnetic properties.

-1 | None. |

0 | Default (16 if doing magnetic CPHF). |

1 | Use single gauge origin – the gauge used to calculate the angular momentum perturbed wavefunctions. |

2 | Use IGAIM method – gauge origin coincident with the nucleus of the integrated atomic regions. |

4 | Use CSGT method. |

8 | Use single gauge origin – the coordinates of which are read in (in Angstroms). |

16 | Use GIAOs. |

IOp(10/46)

Whether to calculate dipole and rotational strengths (VCD).

0 | No (Default). |

1 | Yes. |

2 | No. |

3 | Do only optical rotational using GIAOs. |

4 | Do velocity optical rotation (CPHF for r x Del perturbation). |

5 | Do velocity optical rotation (CPHF for Del perturbation). |

6 | Do velocity optical rotation (CPHF for both Del and r x Del). |

7 | Do length optical rotation with GIAOs (electric field CPHF). |

8 | Do length optical rotation with GIAOs (magnetic field CPHF). |

IOp(10/47)

Whether to do spin-spin coupling constants.

0 | Default (No). |

1 | Yes. |

2 | No. |

3 | Just do the Fermi-contact contribution. |

4 | Yes, but do not print/store the Fermi-Contact contribution. (This assumes that the FC term was done in a previous job step). |

IOp(10/48)

Whether to operate only over perturbations involving active atoms.

0 | Default (for nuclear, compress if overlay 11 did). |

1 | Compress. |

2 | Don’t compress. For SSC or frequencies with frozen atoms, do CPHF for all atoms, even frozen ones. |

3 | Don’t compress, but blank contributions for inactive atoms. |

4 | Compress and store force constants only over active atoms (for ONIOM(MO:MM) Opt=CalcFC with micro-iterations). |

5 | Permute the order of permutations here in order to put QM atoms ahead of electronic embedding atoms. |

10 | Read a list of atoms to include in perturbations. |

000 | Default (100). |

100 | All ONIOM-active, non-frozen nuclei are included in nuclear perturbations. |

200 | Atoms which are not used in the redundant internal coordinate set are not included in the list of perturbations. Saves time for ONIOM-EE non-quadratic Opt=CalcFC. |

0000 | Default (do not include frozen atom coordinates in perturbations unless saving Fock-derivatives). |

1000 | Keep frozen atoms in the perturbation list. |

2000 | Keep frozen atoms in the perturbation list, but zero their B matrices. |

When Fermi-contact spin-spin couplings are read from a previous job step, the same atoms are selected when computing the other terms.

IOp(10/49)

Flag for doing FD polarizability derivatives.

0 | Default (No). |

1 | Yes, do nuclear coord CPHF for Ux and use interchange (production). Default if same basis used to compute both FD polar derivatives and force field. |

2 | Yes, do (static) 2nd order cphf wrt applied field, compute contribution from F(x)/Bx here and use interchange (production). Default if only computing FD polar derivative using this basis. |

3 | Yes, like 2, except use L1110 to produce F(x) and MakeAB for Bx (debugging option). |

4 | Yes, like 1, except use partial interchange (debugging option). |

5 | Yes, do 2nd order CPHF with respect to field and nuclear coord. (debugging option). |

10 | Also do dipole-quadrupole polarizability derivatives. |

100 | Also do dipole-magnetic dipole polarizability derivatives. |

IOp(10/50)

L1003: This controls mode of action of the CPMCSCF. The 3*(Natom-1) linear equations are either solved in turn or an iterative tridiagonal solution of the inverse of Hessian is developed. The first method is very expensive because it scales as 3*(Natom-1)*Nbasis^{2} whereas the second scales as Nbasis^{2}.

0 | Default, same as 3. |

1 | Solve each atom in turn. This is the most accurate approach but it is much more expensive. The recommended value of IOp(7) is 7 (10^{-7}). |

2 | DIIS method with multiple rhs. |

3 | DIIS method with multiple rhs. Forces scalar multiplications. |

4 | Tridiagonal solution of inverse of Hessian. (Default). The recommended value of IOp(7) is 12 (10^{-12}). |

IOp(10/55)

Options for trajectory surface hopping calculations.

See mcscf.F for descriptions.

IOp(10/60-62)

Override standard values of IRadAn, IRanWt, and IRanGd. The default for IOp(60) here is -3, two steps down from default, unless post-SCF gradients or spin-spin couplings are being computed, in which case the same grid is used as in the rest of the calculation.

L1002, L1014: Special values for IOp(60):

0 | Default (-1 for post-SCF gradients and spin-spin coupling, otherwise -3). |

N>1 | Use the specified grid. |

-1 | Use the same grid as the rest of the calculation. |

-2 | Use a grid one step smaller than the general calculation (finegrid for int=ultrafine, sg1 for int=finegrid, etc.). |

-3 | Use a grid two steps smaller than the general calculation. |

-NN0 | A number with two bits for the default in each nuclear case: N = 10(0/1/2/3) + (0/4/8/12) + (0/16/32/48) where the four choices are: 0 = default (same as 3 and global default). 1 = two steps smaller grid for GGAs, one for tau functionals. 2 = one step smaller grid. 3 = full grid. and the 3 terms are for a) CPKS during ground state frequencies, b) CPKS during ground state part of TD and double hybrid frequencies and c) CPTD during TD frequencies. |

-640 | Sets all flags 3 to zero so default of two steps everywhere. |

The values ≤-10 are primarily useful in setting alternate defaults in Default.Route or on the command line.

IOp(10/63)

Change FMM defaults.

0 | Default: Use FMM if turned on globally, use more aggressive cutoffs in Xc integration, use more aggressive cutoffs in integrals and FMM unless doing NFx. |

1 | Turn off FMM here regardless. |

2 | Use FMM if turned on globally. |

3 | Turn FMM on here regardless. |

10 | Use global cutoffs. |

20 | Use local, lower cutoffs suitable only for CPHF/CPKS. |

100 | Turn off FoFCou as well as FMM. |

IOp(10/70)

L1003: Memory estimation scheme:

0 or 1 | Better memory estimation for Â¾ integral transformation (Default). |

2 | Old memory estimation. |

IOp(10/72)

Whether to do frequency-dependant properties.

0 | Default (No, unless both electric and magnetic properties are requested). |

1 | No. |

2 | Yes. |

3 | Also Yes. |

4 | Yes, with formalism for frequency-dependent XC response. |

00 | Update frequency-dependent property file if frequency-dep. calculation is performed. |

10 | Update regardless. |

20 | Do not update. |

IOp(10/73)

Maximum number of CPHF cycles.

0 | Default (1000). |

N | N. |

N<0 | N cycles but return to default if restarting. |

IOp(10/74)

Whether to do non-equilibrium solvation.

0 | Default: Only if frequency-dependant. |

1 | Yes. |

2 | No. |

00 | Default: Not doing state-specific iterations. |

10 | Doing state-specific with non-equilibrium solvation. |

20 | Doing state-specific with equilibrium solvation |

IOp(10/75)

Print during NMR.

0 | Default (1). |

1 | Print tensors and eigenvalues. |

2 | Print eigenvectors as well. |

IOp(10/76)

Override general choice of exchange-correlation frequency dependence.

0 | Use global value for this job step. |

N | Use type N (see IOp(10/88) in overlay 5). |

IOp(10/77)

Test CPHF results by checking the CPHF equations using the complete MO Fock and density derivatives.

0 | Default (No). |

1 | Yes. |

2 | No. |

IOp(10/79)

Stop L1002 at selected points for testing restarts.

MNN | Stop at pass M (default 1), restart point NN. |

IOp(10/80)

Options for trajectory surface hopping calculations. See mcscf.F for descriptions.

IOp(10/81)

Control of number of passes in AXAO.

0 | Default: at most 96 matrices at a time if doing FMM, otherwise no limit. |

-1 | As few passes (as many matrices) as possible. |

N>0 | Do at most N densities per pass. |

N<-1 | Do at least -N passes. |

IOp(10/82)

1 | Force recalculation of MO integrals for MOCPHF. Debugging option. |

IOp(10/87)

Accuracy of 2e integrals.

0 | Default. |

N | 10^{-N}. |

IOp(10/90)

Whether to do correct or approximate CPCIS.

0 | CPCIS is done correctly. |

1 | The A-matrix is neglected, and hence the U-matrices are set equal to the B-matrices (i.e., uncoupled Hartree-Fock is used). |

2 | The U-matrices are set to zero. |

3 | Only a single set of products AX are computed, independent of convergence criteria. Simultaneous solution is implied. |

IOp(10/91)

L1002: Limit IDoFFX.

0 | Default: use the best possible. |

N | Limit IDoFFX<=N, N=9=>IDoFFX=0. |

-N | Force IDoFFX=N. |

IOp(10/92)

Normalization to speed up Raman/ROA:

0 | Default (1). |

1 | Yes. |

2 | No. |

IOp(10/93)

Generate file for AICD. Only works with NMR=CSGT.

0 | Default (No). |

1 | Yes, all orbitals. |

2 | Yes, read in orbitals to include. |

3 | No. |

00 | Default (20). |

10 | Write small elements in matrices. |

20 | Do not write small elements in matrices. |

IOp(10/94)

L1014: Threshold for testing Tx.T.

0 | Default, 5.d-6, continue if test fails. |

N>0 | 1.d-N, die if test fails. |

N<0 | 1.d+N, continue test fails. |

-99 | Default report but but do not die if test fails. |

IOp(10/95)

L1014: Limit IDoFFX.

0 | Default: use the best possible, currently 0. |

N | Limit IDoFFX≤N, N=9=>IDoFFX=0. |

-N | Force IDoFFX=N. |

0x | Default (3 for IDoFFX=6, 1 otherwise). |

1x | Do not optimize the XC matrices update. |

2x | Optimize XC matrices update involving T/Tx, but not G/Gx (this is mostly a debugging option). |

3x | Optimize XC matrices update as much as possible. |

IOp(10/96)

L1014: Whether to compute transition dipole derivatives.

0 | Default (No). |

1 | Yes (results in minor deviations from optimal IDoFFX). |

2 | No. |

IOp(10/100)

L1014: Solution method for CPCIS/CPTD.

0 | Default, same as IOp(10/8) except that separate is done if the convergence is less than the default of 1.d-8. |

-1 | CPHF for each variable in a separate call to LinEq1. |

1 | Expand each variable in a separate expansion space. |

2 | Solve all equations together, possibly reverting to the old (one variable at a time) method in the secondary solution. |

3 | Invert the A matrix directly. |

IOp(10/101)

L1014: Solution method (no interchange).

IOp(10/102)

Diagonal shift preconditioning in CPHF:

-1 | Same as 0. |

0 | No. |

1 | Shift Ea-Ei up to a minimum given by IOp(103). |

2 | Shift all diagonals by the amount given by IOp(103). |

0x | Default (1x). |

1x | Flip the sign of Y shifts. |

2x | Same sign for X and Y. |

IOp(10/103)

Value/threshold for shift during CPHF:

0 | Default (0.1 Hartree). |

N | N/1000 Hartree. |

IOp(10/105)

Shift for predconditioning during CPCIS/CPTD.

-1 | Same as 0. |

0 | No. |

1 | Shift Ea-Ei up to a minimum given by IOp(103). |

2 | Shift all diagonals by the amount given by IOp(103). |

0x | Default (1x). |

1x | Flip the sign of Y shifts. |

2x | Same sign for X and Y. |

IOp(10/106)

Override of IRadAn for just L1014, taking precedence over IOp(60).

IOp(10/107)

Override of IRadAn for just XC2E part of L1014, taking precedence over IOp(60) and IOp(107).

IOp(10/108)

L1014: Stop at selected points for testing restarts.

0 | Default (no stopping). |

BBBNNNN | Stop at restart point N, in batch BBB if applicable. |

IOp(10/109)

L1014: Max number of iterations, overriding IOp(73).

IOp(10/109)

L1014: Max number of iterations, overriding IOp(73).

Last updated on: 21 October 2016. [G16 Rev. A.03]