.. index::
single: Program; RASSCF
single: RASSCF
single: CASSCF
see: CASSCF; RASSCF
.. _TUT\:sec\:rasscf:
:program:`RASSCF` --- A Multi Configurational Self-Consistent Field Program
===========================================================================
One of the central codes in |molcas| is the :program:`RASSCF` program, which
performs multiconfigurational SCF calculations. Both Complete Active Space
(CASSCF) and Restricted Active Space (RASSCF) SCF calculations can be performed
with the :program:`RASSCF` program module :cite:`Roos:92`.
An open shell Hartree--Fock calculation is not possible with the :program:`SCF`
but it can be performed using the :program:`RASSCF` module. An input listing for
a CASSCF calculation of water appears in :numref:`block:rasscf_input`.
:program:`RASSCF` requires orbital information of the system which can be
obtained in two ways. The :kword:`LUMOrb` indicates that the orbitals should be
taken from a user defined orbital file, which is copied to the internal file
INPORB. If this keyword is not given, the program will look for orbitals on the
runfile in the preference order: :file:`RASORB`, :file:`SCFORB` and
:file:`GUESSORB`
.. code-block:: none
:caption: Sample input requesting the :program:`RASSCF` module to calculate the
eight-electrons-in-six-orbitals CASSCF energy of the second excited triplet
state in the second symmetry group of a water molecule in :math:`C_{2v}` symmetry.
:name: block:rasscf_input
&RASSCF
Title= The CASSCF energy of water is calculated using C2v symmetry. 2 3B2 state.
nActEl= 8 0 0
Inactive= 1 0 0 0; Ras2= 3 2 0 1
Symmetry= 2; Spin= 3
CIRoot= 1 2; 2
LumOrb
The :kword:`TITLe` performs the same function as in the previous |molcas|
modules. The keyword :kword:`INACtive` specifies the number of doubly occupied
orbitals in each symmetry that will not be included in the electron excitations
and thus remain doubly occupied throughout the calculation. A diagram of the
complete orbital space available in the :program:`RASSCF` module is given in
:numref:`fig:rasscf_space`.
In our calculation, we have placed the oxygen 1s orbital in the inactive
space using the :kword:`INACtive` keyword. The keyword :kword:`FROZen` can be
used, for example, on heavy atoms to reduce the Basis Set
Superposition Error (BSSE). The corresponding orbitals will then not be
optimized. The :kword:`RAS2` keyword specifies the number of orbitals in each
symmetry to be included in the electron excitations with all possible
occupations allowable. Because the :kword:`RAS1` and :kword:`RAS3` spaces are
zero (not specified in the input in :numref:`block:rasscf_input`) the
:program:`RASSCF` calculation will produce a CASSCF wave function. The
:kword:`RAS2` space is chosen to use all the orbitals available in each
symmetry (except the oxygen 1s orbital). The keyword :kword:`NACTel`
specifies the number of active electrons (8), maximum number of holes in the
Ras1 space (0) and the maximum number of electrons in the Ras3 space (0).
Using the keywords :kword:`RAS1` and/or :kword:`RAS3` to specify orbitals and
specifying none zero numbers of holes/electrons will produce a RASSCF wave
function. We are, therefore, performing an 8in6 CASSCF calculation of
water.
.. table:: Examples of types of wave functions obtainable using the RAS1 and RAS3 spaces in the :program:`RASSCF` module.
:name: tab:RAS1_3
======================== ========================= ========================= =========================
Description Number of holes :kword:`RAS2` Number of electrons
in :kword:`RAS1` orbitals orbitals in :kword:`RAS3` orbitals
======================== ========================= ========================= =========================
SD-CI 2 0 2
SDT-CI 3 0 3
SDTQ-CI 4 0 4
Multi Reference SD-CI 2 :math:`n` 2
Multi Reference SD(T)-CI 3 :math:`n` 2
======================== ========================= ========================= =========================
.. index::
single: Active space
single: CI
There are a number of wave function types that can be performed by manipulating
the :kword:`RAS1` and :kword:`RAS3` spaces. :numref:`tab:RAS1_3` lists
a number of types obtainable. The first three are Configuration
Interaction (CI) wave functions of increasing magnitude culminating with a
Single, Double, Triples and Quadruples (SDTQ) CI. These can become
multi reference if the number of :kword:`RAS2` orbitals is non-zero.
The last type provides some inclusion of the triples excitation by
allowing three holes in the :kword:`RAS1` orbitals but save
computation cost by only allowing double excitations in the :kword:`RAS3`
orbitals.
.. float::
:type: figure
:caption: :program:`RASSCF` orbital space including keywords and electron occupancy ranges.
:name: fig:rasscf_space
.. _tab\:rasscf_space_a:
==== =================================
--- :kword:`DELETED`
0 Virtual
0--2 :kword:`RAS3` orbitals containing
a max. number of electrons
0--2 :kword:`RAS2` orbitals of
arbitrary occupation
0--2 :kword:`RAS1` orbitals containing
a max. number of holes
2 :kword:`INACTIVE`
2 :kword:`FROZEN`
==== =================================
.. index::
single: RASSCF; Symmetry
single: RASSCF; Spin
single: RASSCF; CIroot
single: RASSCF; Level-shift
single: RASSCF; Iterations
The symmetry of the wave function is specified using the
:kword:`SYMMetry` keyword. It specifies the number of the symmetry
subgroup in the calculation. We have chosen the second symmetry
species, :math:`b_2`, for this calculation. We have also chosen the triplet
state using the keyword :kword:`SPIN`. The keyword :kword:`CIROot` has been
used to instruct :program:`RASSCF` to find the second excited state in the
given symmetry and spin. This is achieved by specifying the number of roots,
1, the dimension of the small CI matrix which must be as large as the
highest required root and the number of the required second root.
Only for averaged calculations :kword:`CIROot` needs an additional line
containing the weight of the selected roots (unless equal weights are used for
all states).
As an alternative to giving inactive and active orbital input we can use the
type index input on the :file:`INPORB` and indicate there which type the
different orbitals should belong to: frozen (f), inactive (i), RAS1 (1), RAS2
(2), RAS3 (3), secondary (s), or deleted (d). This approach is very useful when the input
orbitals have been run through :program:`LUSCUS`, which is used to select the
different subspaces. :program:`LUSCUS` will relabel to orbitals according to the
users instructions and the corresponding orbital file, :file:`GvOrb` can be
linked as the :file:`INPORB` in the :program:`RASSCF` program without any
further input.
.. index::
single: Convergence problems; In RASSCF
A level shift was included using the :kword:`LEVShift` keyword
to improve convergence of the calculation. In this case, the calculation
does not converge without the use of the level shift. It is advisable to
perform new calculations with a non-zero :kword:`LEVShift` value (the default
value is 0.5). Another possibility is to increase the maximum number of
iterations for the macro and the super-CI Davidson procedures
from the default values (200,100) using the keyword :kword:`ITERations`.
Sometimes convergence problems might appear when the wave function is
close to fulfill all the convergence criteria. An infrequent but possible
divergence might appear in a calculation starting from orbitals of an already
converged wave function, or in cases where the convergence thresholds
have been decreased below the default values.
Option :kword:`TIGHt` may be useful in those cases. It contains the
thresholds criteria for the Davidson diagonalization procedure. In situations
such as those described above it is recommended to decrease the first
parameter of :kword:`TIGHt` to a value lower than the default, for instance
1.0d-06.
.. index::
single: RASSCF; Output
single: RASSCF; CI coefficients
single: RASSCF; Configurations
single: RASSCF; Natural occupation
:program:`RASSCF` Output
------------------------
The :program:`RASSCF` section of the |molcas| output contains similar
information to the :program:`SCF`
output. Naturally, the fact that we have requested an excited state is
indicated in the output. In fact, both the lowest triplet state and the first
excited state or second root are documented including energies.
For both of these states the CI
configurations with a coefficient greater than 0.05 are printed along
with the partial electron distribution in the active space.
:numref:`block:RASSCF_CI` shows the relevant output for the second
root calculated. There are three configurations with a CI-coefficient
larger than 0.05 and two with very much larger values. The number of the
configuration is given in the first column and the CI-coefficient and
weight are given in the last two columns. The electron occupation of the
orbitals of the first symmetry for each configuration is given under the
"``111``" using "``2``" for a fully occupied orbital and "``u``"
for a singly occupied orbital containing an electron with an up spin.
The down spin electrons are represented with a "``d``". The occupation
numbers of the active space for each symmetry is given below the contributing
configurations. It is important to remember that the active orbitals are
not ordered by any type of criterion within the active space.
.. code-block:: none
:caption: :program:`RASSCF` portion of output relating to CI configurations and electron
occupation of natural orbitals.
:name: block:RASSCF_CI
printout of CI-coefficients larger than .05 for root 2
energy= -75.443990
conf/sym 111 22 4 Coeff Weight
3 22u u0 2 .64031 .40999
4 22u 0u 2 .07674 .00589
13 2u0 2u 2 -.75133 .56450
14 2u0 u2 2 .06193 .00384
19 udu 2u 2 .06489 .00421
Natural orbitals and occupation numbers for root 2
sym 1: 1.986957 1.416217 .437262
sym 2: 1.567238 .594658
sym 4: 1.997668
The molecular orbitals are displayed in a similar fashion to the
:program:`SCF` section of the output except that the energies of the
active orbitals are not defined and therefore are displayed as zero and
the electron occupancies are those calculated by the :program:`RASSCF`
module. In a state average calculation (more than one root calculated),
the MOs will be the natural orbitals corresponding to the state
averaged density matrix (called pseudo-natural orbitals) and the occupation
numbers will be the corresponding eigenvalues. Natural orbital occupation
numbers for each state are printed as shown in :numref:`block:RASSCF_CI`, but
the MOs specific to a given state are not shown in the output. They are,
however, available in the :file:`JOBIPH` file. A number of molecular
properties are also computed for the requested electronic state in a similar
fashion to the :program:`SCF` module.
.. index::
single: Program; RASREAD (obsolete)
single: RASREAD (obsolete)
single: Files; JOBIPH
single: Files; RASORB
single: Convergence problems; In RASSCF
.. _TUT\:sec\:rasread:
Storing and Reading :program:`RASSCF` Orbitals and Wave Functions
-----------------------------------------------------------------
Part of the information stored in the :program:`RASSCF` output file, :file:`JOBIPH`,
for instance the molecular orbitals and occupation numbers can be also found
in an editable file named :file:`RASORB`, which is automatically generated by
:program:`RASSCF`. In case more than one root is used the natural orbitals are
also stored in files :file:`RASORB.1`, :file:`RASORB.2`, etc, up to ten. In such
cases the file :file:`RASORB` contains the averaged orbitals. If more roots
are used the files can be generated using the :kword:`OUTOrbitals` keyword.
The type of orbital produced can be either :kword:`AVERaged`,
:kword:`NATUral`, :kword:`CANOnical` or :kword:`SPIN` (keywords) orbitals.
The :kword:`OUTOrbitals` keyword, combined with the :kword:`ORBOnly` keyword,
can be used to read the :file:`JOBIPH` file and produce
an orbital file, :file:`RASORB`, which can be read by a subsequent
:program:`RASSCF` calculation using the same input section.
The formatted :file:`RASORB` file is useful to operate on the orbitals in order
to obtain appropriate trial orbitals for a subsequent :program:`RASSCF`
calculation. In particular the type index can be changed
directly in the file if the :program:`RASSCF` program has converged to a solution
with wrong orbitals in the active space. The :program:`RASSCF` program
will, however, automatically place the orbital files from the calculation in the
user's home directory under the name :file:`$Project.RasOrb`, etc. In
calculations with spin different from zero the program will also produce the
spin orbital files :file:`$Project.SpdOrb1`, etc for each state. These orbitals
can be used by the program :program:`LUSCUS` to produce spin densities.
:program:`RASSCF` --- Basic and Most Common Keywords
----------------------------------------------------
.. class:: keywordlist
:kword:`SYMMetry`
Symmetry of the wave function (according to :program:`GATEWAY`)
(1 to 8)
:kword:`SPIN`
Spin multiplicity
:kword:`CHARGE`
Molecular charge
:kword:`NACTel`
Three numbers: Total number of active electrons, holes in Ras1, particles in Ras3
:kword:`INACtive`
By symmetry: doubly occupied orbitals
:kword:`RAS1`
By symmetry: Orbitals in space Ras1 (RASSCF)
:kword:`RAS2`
By symmetry: Orbitals in space Ras1 (CASSCF and RASSCF)
:kword:`RAS3`
By symmetry: Orbitals in space Ras1 (RASSCF)
:kword:`CIROot`
Three numbers: number of CI roots, dimension of the CI matrix, relative weights
(typically 1)
:kword:`LUMORB`/:kword:`FILEORB`
use definition of active space from Orbital file