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Subsections
6.8 CASPT2 — A Many Body Perturbation Program
Dynamic correlation energy of a molecular system can be calculated using
the CASPT2 program module in MOLCAS. A CASPT2
calculation gives a second order perturbation estimate of the full CI energy
using the CASSCF wave function of the system.
The program can also perform MultiState CASPT2 calculations (MSCASPT2) in
which different CASPT2 states are coupled using an effective Hamiltonian
computed to second order in perturbation theory. This is necessary in cases
where different CASSCF wave functions are strongly dependent on dynamical
correlation effects. The wave function have to be obtained in a previous
StateAverage CASSCF calculation.
A sample input is given in Figure 6.10. The
FROZen keyword specifies the number of orbitals of each
symmetry which will not be included in the correlation. We have
chosen the RASSCF INACtive orbitals to be frozen
for this calculation (the default is to freeze all core orbitals, so the input
is strictly not needed). The remaining two keywords, CONVergence and
MAXIter, are included with there default values. The
MULTistate keyword is included for clarity even if not needed in this single
state calculation. A single line follows indicating the number of
simultaneously treated CASPT2 roots and the number of the roots in the previous
SACASSCF calculation.
In section the meaning and significance of most of the
features used and printed by the CASPT2 program are explained in the
context of an actual example. We suggest a careful reading of that section
because understanding the results of a CASPT2 calculation is important for
the analysis of problems like intruder states, large coefficients, convergence,
etc.
Figure 6.10:
Sample input requesting the CASPT2 module to calculate the CASPT2 energy of a water molecule in C_{2v} symmetry with one frozen orbital.

&CASPT2
Frozen= 1 0 0 0
Multistate= 1 1
MaxIter= 40
The output of the CASPT2 program begins with the title
from the input as well as the title from the SEWARD input.
It also contains the cartesian coordinates of the molecule and the
CASSCF wave function and orbital specifications. This is followed by
details about the type of Fock and H_{0} operator used and, eventually,
the value of the levelshift parameter employed. It is possible then
to obtain, by input specifications, the quasicanonical orbitals in
which the wave function will be represented. The following CI vector
and occupation number analysis will be performed using the
quasicanonical orbitals.
Two important sections follow. First a detailed report on small energy
denominators, large components, and large energy contributions which will
inform about the reliability of the calculation
(see section )
and finally the CASPT2 property section
including the natural orbitals obtained
as defined in the output and a number of approximated molecular properties.
If the MULTistate option is used, the program will perform one CASPT2
calculation for each one of the selected roots, and finally the complete
effective Hamiltonian containing the selected states will be solved to obtain
the final MSCASPT2 energies and PMCASSCF wave functions [15].
The CASPT2 module needs the integral files in $WorkDir and the
RUNFILE file from the and the JOBIPH file from the
RASSCF module. The orbitals are saved in the PT2ORB file.
The new PMCASSCF wave functions generated in a MSCASPT2 calculation
is saved in the JOBMIX file.
Keyword  Meaning

MULTistate  MultiState CASPT2 calculation: number of roots and roots (Ex. 3 1 2 3)

IMAG  Value for the imaginary shift for the zero order Hamiltonian



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