MOLCAS manual:
Next: 2.7 Analyzing Results: Output
Up: 2. Quickstart Guide for
Previous: 2.5 Input Structure and
Subsections
Start by preparing a file containing the cartesian coordinates of a water molecule.
3
Angstrom
O 0.000000 0.000000 0.000000
H 0.758602 0.000000 0.504284
H 0.758602 0.000000 0.504284
which is given the name water.xyz. In the same directory we prepare
the input for the MOLCAS run. We can name it water.input:
In addition to using an editor to insert atomic coordinates into a file, a coordinate file can be obtained by using
a graphical interface program, for example, the GV module as shown later in this guide.
&GATEWAY
coord=water.xyz
basis=sto3g
&SEWARD
&SCF
The GATEWAY program module combines the molecular geometric of water
(In this case, from the external file, water.xyz) and the basis set definition.
The SEWARD program module then computes the integrals, and SCF program modules
completer the calculation by computing the HartreeFock wave function.
To run the calculation, the following command is used:
molcas water.input f
The file water.log now contains output from the calculation, and the water.err
includes any error messages. In the same directory, other files, including
water.scf.molden or water.grid (if the keyword grid_it is added at end of input file)
that help to analyze the results graphically with the MOLCAS utility molcas gv
or Molden program. Examples of their use are demonstrated below.
In the case of an openshell calculation (UHF or UDFT), the SCF program is again used.
Below, two examples are shown:
 (a)
 A UDFT calculation yielding an approximate doublet by setting the charge to +1, even if they are not pure spin functions:
&GATEWAY
coord=water.xyz
basis=sto3g
&SEWARD
&SCF
charge=+1
uhf; ksdft=b3lyp
 (b)
 A triplet state (using keyword ZSPIn to specify that there are two more than electrons) states
&GATEWAY
coord=water.xyz
basis=sto3g
&SEWARD
&SCF
zspin=2
uhf; ksdft=b3lyp
In the next example, a DFT/B3LYP geometry optimization is performed on the
ground state of the water molecule. Notice that, after &gateway has defined
the coordinates and basis set definition, the EMIL commands >>> Do while
and >>> EndDo are employed to form a loop with the
seward, SLAPAF, and SCF programs until convergence of geometry optimization is reached.
Program seward computes the integrals in atomic basis, SCF computes the DFT energy, and the program
SLAPAF controls the geometry optimization and uses the module ALASKA to compute the gradients
of the energy with respect to the degrees of freedom. SLAPAF generates
the new geometry to continue the iterative structure optimization process and
checks to determine convergence parameters are satisfied notifying MOLCAS and stopping the loop.
&GATEWAY
coord=water.xyz
basis=ANOSMB
>> Do While
&SEWARD
&SCF
ksdft=b3lyp
&SLAPAF
>>> EndDo
The above example illustrates the default situation of optimizing to a minimum geometry without
any further constraint. If other options are required such as determining a transition
state, obtaining a states crossing, or imposing a geometry constraint, specific input
should be added to program SLAPAF.
Figure 2.1:
The acrolein molecule.

One of the most powerful aspects of MOLCAS is the possibility of computing
excited states with multiconfigurational approaches. The next example demonstrates
a calculation of the five lowest singlet roots in a StateAverage (SA) CASSCF calculation
using the RASSCF program. It also illustrates the addition of the CASPT2 program
to determine dynamical correlation which provides accurate electronic energies at the CASPT2 level. The resulting
wave functions are used in the RASSI module to calculate stateinteraction properties such as oscillator strengths and other properties.
&gateway
Coord
8
Acrolein coordinates in Angstrom
O 1.808864 0.137998 0.000000
C 1.769114 0.136549 0.000000
C 0.588145 0.434423 0.000000
C 0.695203 0.361447 0.000000
H 0.548852 1.455362 0.000000
H 0.477859 1.512556 0.000000
H 2.688665 0.434186 0.000000
H 1.880903 1.213924 0.000000
Basis=ANOSMB
Group=Nosym
&SEWARD
&RASSCF
nactel = 6 0 0
inactive= 12
ras2 = 5
ciroot = 5 5 1
&CASPT2
multistate=5 1 2 3 4 5
&RASSI
Nr of Job=1 5; 1 2 3 4 5
EJob
Notice that the Group with the option Nosym has been used
to prevent GATEWAY from identifying the symmetry of the molecule
(C_{s} in this case). Otherwise, the input of the RASSCF program
will have to change to incorporate the classification of the active space
into the corresponding symmetry species. Working with symmetry will be skipped at
this stage, although its use is very convenient in many cases.
A good strategy is to run only GATEWAY and let the program guide you.
The RASSCF input describes the active space employed, composed by
six active electrons distributed in five active orbitals. By indicating
twelve inactive orbitals (always doubly occupied), information
about the total number of electrons and the distribution of the orbitals is then complete.
Five roots will be obtained in the SACASSCF procedurei, and all them will
be computed at the CASPT2 level to obtain the transition energies at the higher
level of theory. Further, the RASSI will compute the transition properties,
in particular, transition dipole moments and oscillator strengths.
MOLCAS incorporates the effects of the solvent using several models.
The most common is the cavitybased reactionfield Polarizable Continuum Model (PCM)
which is invoked by adding the keyword RFinput to the
SEWARD code and is needed to compute the proper integrals.
&GATEWAY
coord=CH4.xyz
Basis=ANOSMB
&SEWARD
RFInput
PCMModel
Solvent=Water
End of RFInput
&RASSCF
Nactel=8 0 0
Inactive=1
Ras2=8
&CASPT2
rfpert
The reaction field is computed in a selfconsistent manner by the
SCF or RASSCF codes and added as a perturbation
to the Hamiltonian in the CASPT2 method with the keyword RFPErt.
Next: 2.7 Analyzing Results: Output
Up: 2. Quickstart Guide for
Previous: 2.5 Input Structure and
