see also section 25.1.

In the case of LT-DF-LCC2/ADC(2) multistate calculations are possible, and it is recommended to calculate more states as needed.

The parameters on the `EOM` card:

`EOM`,*-n.1*, `key1`=*value1*, `key2`=*value2*,...

where *n.1* is the last state of interest, e.g., with `EOM`,*-5.1* the four lowest
excited states will be calculated. The following keywords `key` are possible:

`SINGLET`=*ising*- If set to 1, singlet states will be calculated (default).
`TRIPLET`=*itrip*- If set to 1, triplet states will be calculated (not implemented for ADC(2)).
`EXFILE`=*record.ifil*- Record for converged CIS eigenvectors (default 6100.2).
`SAVE`=*record.ifil*- Record for save of restart information.
`SAVET`=*record.ifil*- Record for restart information for triplet states (if calculated together with singlet states).
`START`=*record.ifil*- Record for restart of previous calculation.
`STARTT`=*record.ifil*- Record for restart of previous calculation (if calculated together with singlet states).
`NSRCH4ST`=*nst*- In the first
*nst*iterations in the Davidson diagonalisation the excited state domains are determined for each basis vector in the Davidson subspace ("search for states") (default 7). `THRLCH`=*thrlch*- threshold for the Davidson procedure. If smaller than zero,
the Davidson procedure is skipped and DIIS is started directly instead
(possible only for restart,
`SAVE`and`START`have to be identical). `THRLCD`=*thrlcd*- threshold for DIIS.
`ADC2`=*adc2*- if , do ADC(2) calculation instead of CC2.
`LTGS`=*ltgs*- if , use LT-DF-LMP2 for the ground state.

Default local approximations are defined according to procedure described in Ref. [3] (Laplace domains).

`INTFRAC`=*fracint*- Rough criterion for specifying eom-domains from laplace-transformed integrals (default 0.8).
`INTEXC`=*excint*- Criterion for specifying important orbitals from laplace-transformed integrals (default 0.999).
`REALFRAC`=*fracreal*- Exact criterion for specifying eom-domains from laplace-transformed integrals (default 0.98).
`FULLFRAC`=*fracfull*- Check for all orbital domains (complete sum over all orbitals) (default 0.95).

To switch to local aproximations calculated according to Ref. [9]
(Boughton-Pulay procedure for excited states), set `INTFRAC` to zero.

Occupied orbital pair lists are calculated from important orbitals (Refs. [1,5]).

`EWEAKPAIR`=*ewpair*- Distance criterion for excited state orbital pairs definition (default 5).
`ALLSTRONG`=*allstr*- Different possibilities for excited state orbital pairs:

0:*ewpair*,*ewpair*,*ewpair*;

1: , ,*ewpair*;

2: ,*ewpair*,*ewpair*(default);

where , are important orbitals and , non-important. More detailed see Ref. [1].

One can try to improve the convergence of iterative procedures by changing following parameters

`PRECOND`=*prec*- Type of preconditioner in LT-DF-LCC2/ADC(2) and DF-CIS:

0: canonical orbital energies;

3: solving linear equations including diagonal part of with MINRES (default). `HSCAL`=*hscl*- Scaling factor for diagonal part of matrix in the case of linear equations preconditioner (default 0.7).

Properties are also activated on the `EOM` card:

`PROPES`=*prop*- States for which properties (dipole moments) should be calculated,
e.g.,
`PROPES=-3.1+5.1-8.1+15.1`2.1 3.1 5.1 6.1 7.1 8.1 15.1 `TRANES`=*tran*- States for which transition moments should be calculated, syntax like for properties. Is not implemented for ADC(2) and for triplet states.
`DENSAVE`=*rec.ifil*- Record, where densities calculated for states
*prop*can be saved (for printing, see 34.4)

By default, orbital un-relaxed properties are computed. In order to calculate also orbital relaxed properties the option `ORBREL` on the `LOCAL` card should be set to 1, *i.e.*,

LOCAL,ORBREL=1This also applies to the calculation of nuclear gradients. Options concerning nuclear gradients, which are also activated on the

`GSONLY`=0 or 1- 1: only ground state gradient is calculated
`GRADSTATE`=*gradstate*- Excited state for which the gradient is to be calculated, e.g.,
`GRADSTATE=2.1`; must be combined with`GSONLY=0` `GRADDIIS`=0 or 1- 0: DIIS after Davidson diagonalization is switched off for all states except
*gradstate* `NOFOLLOWGRAD`=0 or 1- 0: tries to follow a state in a geometry optimization after crossing on the basis of the overlap with eigenvector of previuous geometry;
1: calculate gradient of state number
*gradstate*regardless of crossing `ONLYTOTZLM`=0 or 1- 1: only total, rather than ground- and excited state Lagrange multipliers for orbital variations are computed. Hence, only one set of CPL and CPHF equations need to be solved rather than two. However, orbital relaxed properties are then not available.

manual quickstart instguide update basis

molpro@molpro.net 2018-01-20