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.. index::
single: Program; CASVB
single: CASVB
.. _TUT\:sec\:casvb:
:program:`CASVB` --- A non-orthogonal MCSCF program
===================================================
:program:`CASVB` is a program for carrying out quite general types of
non-orthogonal MCSCF calculations, offering, for example, all the advantages
associated with working within a valence bond formalism.
**Warning:** as for any general MCSCF program, one may experience convergence
problems, (e.g., due to redundant parameters), and the non-orthogonal
optimization of orbitals can furthermore give linear dependency problems.
Several options in :program:`CASVB` can help overcoming these difficulties.
This program can be used in two basic modes:
#. fully variational optimization
#. representation of CASSCF wavefunctions using
overlap- (*relatively inexpensive*) or energy-based criteria.
:program:`CASVB` executes the following logical steps:
Setup of wavefunction information, starting guess generation, one, or several,
optimization steps, various types of analysis of the converged solution.
.. index::
single: CASVB; Input
:program:`CASVB` Input
----------------------
:program:`CASVB` attempts to define defaults for as many input quantities as
possible, so that in the simplest case no input to the :program:`CASVB` module
is required.
Sample input for a CASVB calculation on the lowest singlet state of :math:`\ce{CH_2}`:
.. extractfile:: tutorials/CASVB.CH2.input
&GATEWAY
coord
3
ch2 molecule
C 0.000000 0.000000 0.000000
H 0.000000 0.892226 0.708554
H 0.000000 -0.892226 0.708554
group= x y; basis= sto-3g
&SEWARD
&SCF
&RASSCF
nactel= 6 0 0; inactive= 1 0 0 0; ras2= 3 1 2 0
lumorb
&CASVB
.. index::
single: CASVB; Output
:program:`CASVB` Output
-----------------------
The amount of output in :program:`CASVB` depends heavily on the setting of the
:kword:`PRINT` levels. In case of problems with convergence behaviour it is
recommended to increase these from their rather terse default values.
In the following the main features of the output are outlined, exemplified by
the job in the input above. Initially, all relevant information
from the previous :program:`RASSCF` calculation is recovered from the
:file:`JOBIPH` interface file, after which the valence bond wavefunction
information is summarized, as shown below. Since
spatial configurations have not been specified explicitly in this example, a
single covalent configuration is chosen as default. This gives 5 spin-adapted
VB structures.
::
Number of active electrons : 6
active orbitals : 6
Total spin : 0.0
State symmetry : 1
Spatial VB configurations
-------------------------
Conf. => Orbitals
1 => 1 2 3 4 5 6
Number of VB configurations : 1
VB structures : 5
VB determinants : 20
The output from the following optimization steps summarizes only the most
relevant quantities and convergence information at the default print level. For
the last optimization step, for example, The output below thus
states that the VB wavefunction was found by maximizing the overlap with a
previously optimized CASSCF wavefunction (output by the :program:`RASSCF`
program), and that the spin adaptation was done using the Yamanuchi--Kotani
scheme. Convergence was reached in 7 iterations.
::
-- Starting optimization - step 3 --------
Overlap-based optimization (Svb).
Optimization algorithm: dFletch
Maximum number of iterations: 50
Spin basis: Kotani
-------------------------------------------
Optimization entering local region.
Converged ... maximum update to coefficient: 0.59051924E-06
Final Svb : 0.9978782695
Number of iterations used: 7
Finally in the output below the converged
solution is printed; orbital coefficients (in terms of the active CASSCF MOs)
and structure coefficients. The overlap between orbitals are generally of
interest, and, as also the structures are non-orthogonal, the structure weights
in the total wavefunction. The total VB wavefunction is not symmetry-adapted
explicitly (although one may ensure the correct symmetry by imposing constraints
on orbitals and structure coefficients), so its components in the various
irreducible representations can serve to check that it is physically plausible
(a well behaved solution generally has just one non-vanishing component).
Next follows the one-electron density with natural-orbital analysis, again with
quantities printed in the basis of the active CASSCF MOs.
::
Orbital coefficients :
----------------------
1 2 3 4 5 6
1 0.43397359 -0.43397359 -0.79451779 -0.68987187 -0.79451780 -0.68987186
2 -0.80889967 0.80889967 -0.05986171 -0.05516284 -0.05986171 -0.05516284
3 0.00005587 -0.00005587 0.20401015 -0.20582094 0.20401016 -0.20582095
4 0.39667145 0.39667145 0.00000000 0.00000000 0.00000000 0.00000000
5 -0.00000001 -0.00000001 -0.53361427 -0.65931951 0.53361425 0.65931952
6 0.00000000 0.00000000 0.19696124 -0.20968879 -0.19696124 0.20968879
Overlap between orbitals :
--------------------------
1 2 3 4 5 6
1 1.00000000 -0.68530352 -0.29636622 -0.25477647 -0.29636623 -0.25477647
2 -0.68530352 1.00000000 0.29636622 0.25477647 0.29636623 0.25477646
3 -0.29636622 0.29636622 1.00000000 0.81994979 0.35292419 0.19890631
4 -0.25477647 0.25477647 0.81994979 1.00000000 0.19890634 0.04265679
5 -0.29636623 0.29636623 0.35292419 0.19890634 1.00000000 0.81994978
6 -0.25477647 0.25477646 0.19890631 0.04265679 0.81994978 1.00000000
Structure coefficients :
------------------------
0.00000000 0.00000001 0.09455957 0.00000000 -0.99551921
Saving VB wavefunction to file VBWFN.
Saving VB CI vector to file JOBIPH.
Svb : 0.9978782695
Evb : -38.4265149062
Chirgwin-Coulson weights of structures :
----------------------------------------
VB spin+space (norm 1.00000000) :
0.00000000 0.00000000 -0.00211737 0.00000000 1.00211737
VB spin only (norm 0.38213666) :
0.00000000 0.00000000 0.00894151 0.00000000 0.99105849
Symmetry contributions to total VB wavefunction :
-------------------------------------------------
Irreps 1 to 4 : 0.10000000E+01 0.15118834E-17 0.17653074E-17 0.49309519E-17
Energies for components > 1d-10 :
---------------------------------
Irreps 1 to 4 : -0.38426515E+02 0.00000000E+00 0.00000000E+00 0.00000000E+00
One-electron density :
----------------------
1 2 3 4 5 6
1 1.98488829 -0.00021330 0.00011757 0.00000000 0.00000000 0.00000000
2 -0.00021330 1.90209222 -0.00006927 0.00000000 0.00000000 0.00000000
3 0.00011757 -0.00006927 0.02068155 0.00000000 0.00000000 0.00000000
4 0.00000000 0.00000000 0.00000000 0.09447774 0.00000000 0.00000000
5 0.00000000 0.00000000 0.00000000 0.00000000 1.97572540 -0.00030574
6 0.00000000 0.00000000 0.00000000 0.00000000 -0.00030574 0.02213479
Natural orbitals :
------------------
1 2 3 4 5 6
1 -0.99999668 0.00000000 0.00257629 0.00000000 0.00000000 0.00005985
2 0.00257628 0.00000000 0.99999668 0.00000000 0.00000000 -0.00003681
3 -0.00005995 0.00000000 -0.00003666 0.00000000 -0.00000001 -1.00000000
4 0.00000000 0.00000000 0.00000000 1.00000000 0.00000001 0.00000000
5 0.00000000 0.99999999 0.00000000 0.00000000 0.00015650 0.00000000
6 0.00000000 -0.00015650 0.00000000 -0.00000001 0.99999999 -0.00000001
Occupation numbers :
--------------------
1 2 3 4 5 6
1 1.98488885 1.97572545 1.90209167 0.09447774 0.02213475 0.02068154
.. index::
single: CASVB; Plotting
Viewing and plotting VB orbitals
--------------------------------
In many cases it can be helpful to view the shape of the converged valence bond
orbitals. |molcas| therefore provides two facilities for doing this. For the
Molden program, an interface file is generated at the end of each
:program:`CASVB` run (see also :numref:`UG:sec:Molden`). Alternatively a
:program:`CASVB` run may be followed by :program:`RASSCF`
(:numref:`UG:sec:rasscf`) and :program:`GRID_IT`
(:numref:`UG:sec:gridit`) with the :kword:`VB` specification, in order to
generate necessary files for viewing with :program:`LUSCUS`.
|
