.. index::
   single: High Quality

.. _TUT\:sec\:rp_wf:

High quality wave functions at optimized structures
===================================================

.. only:: html

  .. contents::
     :local:
     :backlinks: none

Here we will give an example of how geometrical structures obtained at
one level of theory can be used in an analysis at high quality wave functions.
:numref:`tab:tsgeo` compiles the obtained CASSCF geometries for
the dimethylcarbene to propene reaction (see :numref:`fig:reaction`).
They can be compared to the MP2 geometries :cite:`Ford:97`.
The overall agreement is good.

.. figure:: reaction.*
   :name: fig:reaction
   :width: 75%
   :align: center

   Dimethylcarbene to propene reaction path

The wave function at each of the geometries was
proved to be almost a single configuration. The second configuration in
all the cases contributed by less than 5% to the weight of the wave
function. It is a double excited replacement. Therefore, although
MP2 is not generally expected to describe properly a bond formation
in this case its behavior seems to be validated. The larger discrepancies
appear in the carbon-carbon distances in the dimethylcarbene and in
the transition state. On one hand the basis set used in the present
example were small; on the other hand there are indications that
the MP2 method overestimates the hyper conjugation effects present
in the dimethylcarbene :cite:`Ford:97`. :numref:`fig:carbene` displays
the dimethylcarbene with indication of the employed labeling.

.. figure:: carbene.*
   :name: fig:carbene
   :width: 50%
   :align: center

   Dimethylcarbene atom labeling

.. table:: Bond distances (Å) and bond angles (deg) of
           dimethylcarbene, propene, and their transition state\ [#a]_
   :name: tab:tsgeo

   ========== ============================= ============================= ============================= ============================= ============================= ============================= ============================= ============================= =============================
   |zws|      :math:`\ce{C{1}C{3}}`         :math:`\ce{C{1}C{2}}`         :math:`\ce{C{2}C{1}C{3}}`     :math:`\ce{C{1}C{3}H{6}}`     :math:`\ce{C{2}C{1}C{3}H{6}}` :math:`\ce{C{2}H{5}}`         :math:`\ce{C{1}H{5}}`         :math:`\ce{C{1}C{2}H{5}}`     :math:`\ce{C{3}C{1}C{2}H{5}}`
   ========== ============================= ============================= ============================= ============================= ============================= ============================= ============================= ============================= =============================
   *Dimethylcarbene*
   ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
   CAS\ [#b]_ 1.497                         1.497                         110.9                         102.9                         88.9                          1.099                                                       102.9                         88.9
   MP2\ [#c]_ 1.480                         1.480                         110.3                          98.0                         85.5                          1.106                                                        98.0                         85.5
   *Transition structure*
   ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
   CAS\ [#b]_ 1.512                         1.394                         114.6                         106.1                         68.6                          1.287                         1.315                          58.6                         76.6
   MP2\ [#c]_ 1.509                         1.402                         112.3                         105.1                         69.2                          1.251                         1.326                          59.6                         77.7
   *Propene*
   ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
   CAS\ [#b]_ 1.505                         1.344                         124.9                         110.7                         59.4
   MP2\ [#c]_ 1.501                         1.338                         124.4                         111.1                         59.4
   ========== ============================= ============================= ============================= ============================= ============================= ============================= ============================= ============================= =============================

.. [#a] :math:`\ce{C{1}}`, carbenoid center; :math:`\ce{C{2}}`, carbon which loses the hydrogen :math:`\ce{H{5}}`. See :numref:`fig:carbene`.
.. [#b] Present results. CASSCF, ANO-S C[3s2p1d], H[2d1p]. Two electrons in two orbitals.
.. [#c] MP2 6-31G(2p,d), Ref. :cite:`Ford:97`.

.. index::
   single: Geometry

The main structural effects occurring during the reaction can be observed
displayed in :numref:`tab:tsgeo`. As the rearrangement starts out one
hydrogen atom (:math:`\ce{H{5}}`) moves in a plane almost perpendicular to the plane
formed by the three carbon atoms while the remaining two hydrogen atoms
on the same methyl group swing very rapidly into a nearly planar
position (see :numref:`fig:reaction`).
As the :math:`\pi` bond is formed we observe
a contraction of the :math:`\ce{C{1}-C{2}}` distance. In contrast, the spectator
methyl group behaves as a rigid body. Their parameters were
not compiled here but it rotates and bends slightly :cite:`Ford:97`. Focusing
on the second half reaction, the moving hydrogen atom rotates into the
plane of the carbon atoms to form the new :math:`\ce{C{1}-H{5}}` bond. This movement
is followed by a further shortening of the preformed :math:`\ce{C{1}-C{2}}` bond,
which acquires the bond distance of a typical double carbon bond, and
smaller adjustments in the positions of the other atoms. The structures
of the reactant, transition state, and product are shown in
:numref:`fig:reaction`.

As was already mentioned we will apply now higher-correlated methods
for the reactant, product, and transition state system at the CASSCF
optimized geometries to account for more accurate relative energies.
In any case a small basis set has been used and therefore the goal is
not to be extremely accurate. For more complete results see Ref.
:cite:`Ford:97`. We are going to perform calculations with the
MP2, MRCI, ACPF, CASPT2, CCSD, and CCSD(T) methods.

Starting with dimethylcarbene, we will use the following input file:

.. extractfile:: advanced/CCSDT.dimethylcarbene.input

  &SEWARD &END
  Title
   Dimethylcarbene singlet C2-sym
   CASSCF(ANO-VDZP) opt geometry
  Symmetry
   XY
  Basis set
  C.ANO-S...3s2p1d.
  C1              .0000000000         .0000000000        1.2019871414
  C2              .0369055124        2.3301037548        -.4006974719
  End of basis
  Basis set
  H.ANO-S...2s1p.
  H1             -.8322309260        2.1305589948       -2.2666729831
  H2             -.7079699536        3.9796589218         .5772009623
  H3             2.0671154914        2.6585385786        -.6954193494
  End of basis
  PkThrs
   1.0E-10
  End of input

  &SCF &END
  Title
  Dmc
  Occupied
  7 5
  End of input

  &RASSCF &END
  Title
  Dmc
  Symmetry
   1
  Spin
   1
  Nactel
   2  0  0
  Inactive
   6  5
  Ras2
   1  1
  Thrs
  1.0E-05,1.0E-03,1.0E-03
  Iteration
  50,25
  LumOrb
  End of input

  &CASPT2 &END
  Title
  Dmc
  LRoot
  1
  Frozen
   2  1
  End of input

  &MOTRA &END
  Title
  Dmc
  Frozen
   2  1
  JobIph
  End of input

  &GUGA &END
  Title
  Dmc
  Electrons
  18
  Spin
   1
  Inactive
   4  4
  Active
   1  1
  Ciall
   1
  Print
   5
  End of input

  &MRCI &END
  Title
  Dimethylcarbene
  SDCI
  End of input

  &MRCI &END
  Title
  Dimethylcarbene
  ACPF
  End of input

  * Now we generate the single ref. function
  * for coupled-cluster calculations

  &RASSCF &END
  Title
  Dmc
  Symmetry
   1
  Spin
   1
  Nactel
   0  0  0
  Inactive
   7  5
  Ras2
   0  0
  Thrs
  1.0E-05,1.0E-03,1.0E-03
  Iteration
  50,25
  LumOrb
  OutOrbitals
   Canonical
  End of input

  &MOTRA &END
  Title
  Dmc
  Frozen
   2  1
  JobIph
  End of input

  &CCSDT &END
  Title
   Dmc
  CCT
  Iterations
   40
  Triples
   2
  End of input

.. index::
   single: MP2
   single: Program; MBPT2
   single: CCSD
   single: CCSD(T)
   single: Program; CCSORT
   single: Program; CCSD
   single: Program; CCT3
   single: Program; CCSDT
   single: ACPF
   single: Program; CPF
   single: MRCI
   single: Program; MRCI
   single: Option; Canonical
   single: RASSCF; Canonical

Observe in the previous input that we have generated a multiconfigurational
wave function for CASPT2, MRCI, and ACPF wave functions but a single configuration
reference wave function (using :program:`RASSCF` program with the options
:kword:`OUTOrbitals` and :kword:`CANOnical`)
for the CCSD and CCSD(T) wave functions. Notice also
that to compute a multiconfigurational ACPF wave function we have to use
the :program:`MRCI` program, not the :program:`CPF` module which does not accept
more than one single reference. In all the highly correlated
methods we have frozen the three carbon core orbitals because of the reasons
already explained in section :ref:`TUT:sec:x2`. For MRCI, ACPF, CCSD, and CCSD(T)
the freezing is performed in the :program:`MOTRA` step.

.. index::
   single: Reference space
   single: Active space

One question that can be addressed is which is the proper reference space
for the multiconfigurational calculations. As was explained when we selected
the active space for the geometry optimizations, we performed several tests
at different stages in the reaction path and observed that the smallest
meaningful active space, two electrons in two orbitals, was sufficient
in all the cases. We can come back to this problem here to select the
reference for CASPT2, MRCI, and ACPF methods. The simple analysis of the
SCF orbital energies shows that in dimethylcarbene, for instance, the
orbital energies of the :math:`\ce{C-H}` bonds are close to those of the :math:`\ce{C-C}` :math:`\sigma`
bonds and additionally those orbitals are strongly mixed along
the reaction path. A balanced active space including all orbitals necessary
to describe the shifting H-atom properly would require a full valence
space of 18 electrons in 18 orbitals. This is not a feasible space, therefore
we proceed with the minimal active space and analyze later the quality
of the results. The CASSCF wave function will then include for dimethylcarbene
and the transition state structure the :math:`(\sigma)^2(\pi)^0` and
:math:`(\sigma)^0(\pi)^2` configurations correlating the non-bonded electrons
localized at the carbenoid center where as for propene the active space
include the equivalent valence :math:`\pi` space.

.. index::
   single: GUGA
   single: Program; GUGA
   single: GUGA; Electrons
   single: GUGA; Active
   single: GUGA; Inactive
   single: GUGA; Ciall
   single: Option; Ciall
   single: Option; Electrons
   single: Option; Symmetry in GUGA

The :program:`GUGA` input must be built carefully. There are several
ways to specify the reference configurations for the following methods.
First, the keyword :kword:`ELECtrons` refers to the total number of
electrons that are going to be correlated, that is, all except those
frozen in the previous :program:`MOTRA` step.
Keywords :kword:`INACtive` and
:kword:`ACTIve` are optional and describe the number of inactive
(occupation two in all the reference configurations) and active
(varying occupation number in the reference configurations) orbitals
of the space. Here :kword:`ACTIve` indicates one orbital of each
of the symmetries. The following keyword :kword:`CIALl` indicates
that the reference space will be the full CI within the subspace
of active orbitals. It must be always followed by symmetry index
(number of the irrep) for the resulting wave function, one here.

For the transition state structure we do not impose any symmetry
restriction, therefore the calculations are performed in the :math:`C_1` group
with the input file:

.. extractfile:: advanced/CCSDT.C1.input

  &SEWARD &END
  Title
   Dimethylcarbene to propene
   Transition State C1 symmetry
   CASSCF (ANO-VDZP) opt geometry
  Basis set
  C.ANO-S...3s2p1d.
  End of basis
  Basis set
  H.ANO-S...2s1p.
  End of basis
  PkThrs
   1.0E-10
  End of input

  &SCF &END
  Title
   Ts
  Occupied
   12
  End of input

  &MBPT2 &END
  Title
   Ts
  Frozen
   3
  End of input

  &RASSCF &END
  Title
   Ts
  Symmetry
   1
  Spin
   1
  Nactel
   2  0  0
  Inactive
   11
  Ras2
   2
  Iteration
  50,25
  LumOrb
  End of input

  &CASPT2 &END
  Title
   Ts
  LRoot
   1
  Frozen
   3
  End of input

  &MOTRA &END
  Title
   Ts
  Frozen
   3
  JobIph
  End of input

  &GUGA &END
  Title
   Ts
  Electrons
   18
  Spin
   1
  Inactive
   8
  Active
   2
  Ciall
   1
  Print
   5
  End of input

  &MRCI &END
  Title
   Ts
  SDCI
  End of input

  &MRCI &END
  Title
   Ts
  ACPF
  End of input

  &RASSCF &END
  Title
   Ts
  Symmetry
   1
  Spin
   1
  Nactel
   0  0  0
  Inactive
   12
  Ras2
   0
  Iteration
  50,25
  LumOrb
  OutOrbitals
   Canonical
  End of input

  &MOTRA &END
  Title
   Ts
  Frozen
   3
  JobIph
  End of input

  &CCSDT &END
  Title
   Ts
  CCT
  Iterations
   40
  Triples
   2
  End of input

Finally we compute the wave functions for the product, propene, in the
:math:`C_s` symmetry group with the input:

.. extractfile:: advanced/CCSDT.Cs.input

  &SEWARD &END
  Title
   Propene singlet Cs-sym
   CASSCF(ANO-VDZP) opt geometry
  Symmetry
   Z
  Basis set
  C.ANO-S...3s2p1d.
  C1            -2.4150580342         .2276105054         .0000000000
  C2              .0418519070         .8733601069         .0000000000
  C3             2.2070668305        -.9719171861         .0000000000
  End of basis
  Basis set
  H.ANO-S...2s1p.
  H1            -3.0022907382       -1.7332097498         .0000000000
  H2            -3.8884900111        1.6454331428         .0000000000
  H3              .5407865292        2.8637419734         .0000000000
  H4             1.5296107561       -2.9154199848         .0000000000
  H5             3.3992878183        -.6985812202        1.6621549148
  End of basis
  PkThrs
   1.0E-10
  End of input

  &SCF &END
  Title
  Propene
  Occupied
  10 2
  End of input

  &MBPT2 &END
  Title
   Propene
  Frozen
   3 0
  End of input

  &RASSCF &END
  Title
  Propene
  Symmetry
  1
  Spin
  1
  Nactel
   2  0  0
  Inactive
  10  1
  Ras2
   0  2
  Thrs
  1.0E-05,1.0E-03,1.0E-03
  Iteration
  50,25
  LumOrb
  End of input

  &CASPT2 &END
  Title
  Propene
  LRoot
  1
  Frozen
   3  0
  End of input

  &MOTRA &END
  Title
  Propene
  Frozen
   3  0
  JobIph
  End of input

  &GUGA &END
  Title
  Propene
  Electrons
  18
  Spin
   1
  Inactive
   7  1
  Active
   0  2
  Ciall
   1
  Print
   5
  End of input

  &MRCI &END
  Title
  Propene
  SDCI
  End of input

  &MRCI &END
  Title
  Propene
  ACPF
  End of input

  &RASSCF &END
  Title
  Propene
  Symmetry
  1
  Spin
  1
  Nactel
   0  0  0
  Inactive
  10  2
  Ras2
   0  0
  Thrs
  1.0E-05,1.0E-03,1.0E-03
  Iteration
  50,25
  LumOrb
  OutOrbitals
   Canonical
  End of input

  &MOTRA &END
  Title
  Propene
  Frozen
   3  0
  JobIph
  End of input

  &CCSDT &END
  Title
   Propene
  CCT
  Iterations
   40
  Triples
   2
  End of input

:numref:`tab:rpener` compiles the total and relative energies
obtained for the studied reaction at the different levels of
theory employed.

.. index::
   single: Barrier height
   single: Exothermicity
   single: Reaction path

.. float::
   :type: table
   :name: tab:rpener
   :caption-top:
   :caption: Absolute (au) and relative (kcal/mol, in parentheses) energies obtained at the different
             theory levels for the reaction path from dimethylcarbene to propene.

   .. _tab_rpener_a:

   ========= ============== ============== ============== ==============
   Single configurational methods
   ---------------------------------------------------------------------
   |zws|     RHF            MP2            CCSD           CCSD(T)
   ========= ============== ============== ============== ==============
   *Dimethylcarbene*
   ---------------------------------------------------------------------
   \         |-|\117.001170 |-|\117.392130 |-|\117.442422 |-|\117.455788
   *Transition state structure*
   ---------------------------------------------------------------------
   \         |-|\116.972670 |-|\117.381342 |-|\117.424088 |-|\117.439239
   BH\ [#d]_ (17.88)        (6.77)         (11.50)        (10.38)
   *Propene*
   ---------------------------------------------------------------------
   \         |-|\117.094700 |-|\117.504053 |-|\117.545133 |-|\117.559729
   EX\ [#e]_ (|-|\58.69)    (|-|\70.23)    (|-|\64.45)    (|-|\65.22)
   ========= ============== ============== ============== ==============

   .. _tab_rpener_b:

   ========= ============== ============== ============== ==============
   Multiconfigurational methods
   ---------------------------------------------------------------------
   |zws|     CASSCF         CASPT2         SD-MRCI+Q      ACPF
   ========= ============== ============== ============== ==============
   *Dimethylcarbene*
   ---------------------------------------------------------------------
   \         |-|\117.020462 |-|\117.398025 |-|\117.447395 |-|\117.448813
   *Transition state structure*
   ---------------------------------------------------------------------
   \         |-|\116.988419 |-|\117.383017 |-|\117.430951 |-|\117.432554
   BH\ [#d]_ (20.11)        (9.42)         (10.32)        (10.20)
   *Propene*
   ---------------------------------------------------------------------
   \         |-|\117.122264 |-|\117.506315 |-|\117.554048 |-|\117.554874
   EX\ [#e]_ (|-|\63.88)    (|-|\67.95)    (|-|\66.93)    (|-|\66.55)
   ========= ============== ============== ============== ==============

   .. [#d] Barrier height. Needs to be corrected with the zero point vibrational correction.
   .. [#e] Exothermicity. Needs to be corrected with the zero point vibrational correction.

We can discuss now the quality of the results obtained and their
reliability (for a more careful discussion of the accuracy of
quantum chemical calculations see Ref. :cite:`Taylor:92b`).
In first place we have to consider that a valence
double-zeta plus polarization basis set is somewhat small to obtain
accurate results. At least a triple-zeta quality would be required.
The present results have, however, the goal to serve as an example.
We already pointed out that the CASSCF geometries were very similar
to the MP2 reported geometries :cite:`Ford:97`. This fact validates
both methods. MP2 provides remarkably accurate geometries using
basis sets of triple-zeta quality, as in Ref. :cite:`Ford:97`, in
situations were the systems can be described as singly configurational,
as the CASSCF calculations show. The Hartree--Fock configuration has
a contribution of more than 95% in all three structures, while the
largest weight for another configuration appears in propene for
:math:`(\pi)^0(\pi^*)^2` (4.2%).

.. index::
   single: MRCI
   single: Program; MRCI

The MRCI calculations provide also one test of the validity of the
reference wave function. For instance, the MRCI output for propene is: ::

                 FINAL RESULTS FOR STATE NR   1
   CORRESPONDING ROOT OF REFERENCE CI IS NR:  1
              REFERENCE CI ENERGY: -117.12226386
           EXTRA-REFERENCE WEIGHT:     .11847074
              CI CORRELATION ENERGY:    -.38063043
                        CI ENERGY: -117.50289429
              DAVIDSON CORRECTION:    -.05115380
               CORRECTED ENERGY: -117.55404809
                    ACPF CORRECTION:    -.04480105
                 CORRECTED ENERGY: -117.54769535

        CI-COEFFICIENTS LARGER THAN  .050
    NOTE: THE FOLLOWING ORBITALS WERE FROZEN
    ALREADY AT THE INTEGRAL TRANSFORMATION STEP
    AND DO NOT EXPLICITLY APPEAR:
          SYMMETRY:   1   2
        PRE-FROZEN:   3   0
    ORDER OF SPIN-COUPLING: (PRE-FROZEN, NOT SHOWN)
                            (FROZEN, NOT SHOWN)
                             VIRTUAL
                             ADDED VALENCE
                             INACTIVE
                             ACTIVE

    ORBITALS ARE NUMBERED WITHIN EACH SEPARATE SYMMETRY.


        CONFIGURATION     32   COEFFICIENT  -.165909   REFERENCE
   SYMMETRY             1  1  1  1  1  1  1  2  2  2
   ORBITALS             4  5  6  7  8  9 10  1  2  3
   OCCUPATION           2  2  2  2  2  2  2  2  0  2
   SPIN-COUPLING        3  3  3  3  3  3  3  3  0  3


        CONFIGURATION     33   COEFFICIENT  -.000370   REFERENCE
   SYMMETRY             1  1  1  1  1  1  1  2  2  2
   ORBITALS             4  5  6  7  8  9 10  1  2  3
   OCCUPATION           2  2  2  2  2  2  2  2  1  1
   SPIN-COUPLING        3  3  3  3  3  3  3  3  1  2

        CONFIGURATION     34   COEFFICIENT   .924123   REFERENCE
   SYMMETRY             1  1  1  1  1  1  1  2  2  2
   ORBITALS             4  5  6  7  8  9 10  1  2  3
   OCCUPATION           2  2  2  2  2  2  2  2  2  0
   SPIN-COUPLING        3  3  3  3  3  3  3  3  3  0
  **************************************************************

.. Note: contains a nbsp

The Hartree--Fock configuration contributes to the
MRCI configuration with a weight of 85.4%, while the next configuration
contributes by 2.8%. Similar conclusions can be obtained analyzing the
ACPF results and for the other structures. We will keep the MRCI results
including the Davidson correction (MRCI+Q) which corrects for the
size-inconsistency of the truncated CI expansion :cite:`Taylor:92b`.

For CASPT2 the evaluation criteria are commented in
section :ref:`TUT:sec:excited`. The portion of the :program:`CASPT2` output for
propene is: ::

        Reference energy:        -117.1222638304
        E2 (Non-variational):       -.3851719971
        E2 (Variational):           -.3840516039
        Total energy:            -117.5063154343
        Residual norm:               .0000000000
        Reference weight:            .87905

        Contributions to the CASPT2 correlation energy
        Active & Virtual Only:          -.0057016698
        One Inactive Excited:           -.0828133881
        Two Inactive Excited:           -.2966569393


  ----------------------------------------------------------------------------
  Report on small energy denominators, large components, and large energy contributions.
  The ACTIVE-MIX index denotes linear combinations which gives ON expansion functions
    and makes H0 diagonal within type.
  DENOMINATOR: The (H0_ii - E0) value from the above-mentioned diagonal approximation.
  RHS value: Right-Hand Side of CASPT2 Eqs.
  COEFFICIENT: Multiplies each of the above ON terms in the first-order wave function.
  Thresholds used:
          Denominators:  .3000
            Components:  .0250
  Energy contributions:  .0050

  CASE SYMM ACTIVE  NON-ACT IND    DENOMINATOR  RHS VALUE  COEFFICIENT CONTRIBUTION
  AIVX  1  Mu1.0003 In1.004 Se1.022  2.28926570 .05988708  -.02615995  -.00156664

.. Note: contains a nbsp

.. index::
   single: CASPT2
   single: Program; CASPT2

The weight of the CASSCF reference to the first-order wave function is
here 87.9%, very close to the weights obtained for the dimethylcarbene and
the transition state structure,
and there is only a small contribution to the wave function and energy
which is larger than the selected thresholds. This should not be considered as a
intruder state, but as a contribution from the fourth inactive orbital which
could be, eventually, included in the active space. The contribution to the
second-order energy in this case is smaller than 1 kcal/mol. It can be observed
that the same contribution shows up for the transition state structure but not
for the dimethylcarbene. In principle this could be an indication that a larger
active space, that is, four electrons in four orbitals, would give a slightly
more accurate CASPT2 energy. The present results will probably overestimate
the second-order energies for the transition state structure and the propene,
leading to a slightly smaller activation barrier and a slightly larger
exothermicity, as can be observed in :numref:`tab:rpener`. The orbitals
pointed out as responsible for the large contributions in propene are the
fourth inactive and 22nd secondary orbitals of the first symmetry. They are
too deep and too high, respectively, to expect that an increase in the active
space could in fact represent a great improvement in the CASPT2 result.
In any case we tested for four orbitals-four electrons CASSCF/CASPT2 calculations
and the results were very similar to those presented here.

.. index::
   single: CCSD
   single: CCSD(T)
   single: Program; CCSORT
   single: Program; CCSD
   single: Program; CCT3
   single: Program; CCSDT

Finally we can analyze the so-called :math:`\tau_1`\-diagnostic :cite:`Lee:89`
for the coupled-cluster wave functions. :math:`\tau_1` is defined for closed-shell
coupled-cluster methods as the Euclidean norm of the vector of :math:`T_1`
amplitudes normalized by the number of electrons correlated:
:math:`\tau_1 = \lVert T_1\Vert/N_{\text{el}}^{1/2}`.
In the output of the :program:`CCSD` program we have: ::

        Convergence after  17  Iterations


        Total energy (diff) :    -117.54513288       -.00000061
        Correlation energy  :       -.45043295
        E1aa   contribution :        .00000000
        E1bb   contribution :        .00000000
        E2aaaa contribution :       -.04300448
        E2bbbb contribution :       -.04300448
        E2abab contribution :       -.36442400


   Five largest amplitudes of :T1aa
    SYMA   SYMB   SYMI   SYMJ     A      B      I      J     VALUE
      2      0      2      0      4      0      2      0     -.0149364994
      2      0      2      0      2      0      2      0      .0132231037
      2      0      2      0      8      0      2      0     -.0104167047
      2      0      2      0      7      0      2      0     -.0103366543
      2      0      2      0      1      0      2      0      .0077537734
   Euclidean norm is :      .0403635306

   Five largest amplitudes of :T1bb
    SYMA   SYMB   SYMI   SYMJ     A      B      I      J     VALUE
      2      0      2      0      4      0      2      0     -.0149364994
      2      0      2      0      2      0      2      0      .0132231037
      2      0      2      0      8      0      2      0     -.0104167047
      2      0      2      0      7      0      2      0     -.0103366543
      2      0      2      0      1      0      2      0      .0077537734
   Euclidean norm is :      .0403635306

.. Note: contains a nbsp

In this case T1aa and T1bb are identical because we are computing a
closed-shell singlet state. The five largest :math:`T_1` amplitudes are
printed, as well as the Euclidean norm. Here the number of correlated
electrons is 18, therefore the value for the :math:`\tau_1` diagnostic is 0.01.
This value can be considered acceptable as evaluation of the
quality of the calculation. The use of :math:`\tau_1` as a diagnostic is
based on an observed empirical correlation: larger values give poor
CCSD results for molecular structures, binding energies, and
vibrational frequencies :cite:`Lee:92`. It was considered that values
larger than 0.02 indicated that results from single-reference electron
correlation methods limited to single and double excitations should be
viewed with caution.

There are several considerations concerning the :math:`\tau_1` diagnostic
:cite:`Lee:89`. First, it is only valid within the frozen core
approximation and it was defined for coupled-cluster procedures
using SCF molecular orbitals in the reference function. Second, it is
a measure of the importance of non-dynamical electron correlation effects
and not of the degree of the multireference effects. Sometimes the two
effects are related, but not always (see discussion in Ref. :cite:`Lee:92`).
Finally, the performance of the CCSD(T) method is reasonably good even
in situations where :math:`\tau_1` has a value as large as 0.08.
In conclusion, the use of :math:`\tau_1` together with other wave function
analysis, such as explicitly examining the largest :math:`T_1` and :math:`T_2`
amplitudes, is the best approach to evaluate the quality of the
calculations but this must be done with extreme caution.

As the present systems are reasonably well described by a single
determinant reference function there is no doubt that the CCSD(T)
method provides the most accurate results. Here CASPT2, MRCI+Q,
ACPF, and CCSD(T) predict the barrier height from the reactant
to the transition state with an accuracy better than 1 kcal/mol.
The correspondence is somewhat worse, about 3 kcal/mol, for the
exothermicity. As the difference is largest for the CCSD(T) method
we may conclude than triple and higher order excitations are of
importance to achieve a balanced correlation treatment, in particular
with respect to the partially occupied :math:`\pi^*` orbital at the
carbenoid center. It is also noticeable that the relative MP2
energies appear to be shifted about 3--4 kcal/mol towards lower
values. This effect may be due to the overestimation of the
hyper-conjugation effect which appears to be strongest in dimethylcarbene
:cite:`Matzinger:95,Ford:97`.

.. index::
   single: Zero Point correction

Additional factors affecting the accuracy of the results obtained
are the zero point vibrational energy correction and, of course,
the saturation of the one particle basis sets. The zero point
vibrational correction could be computed by performing a numerical
harmonic vibrational analysis at the CASSCF level using |molcas|
At the MP2 level :cite:`Ford:97` the
obtained values were |-|\1.1 kcal/mol and 2.4 kcal/mol for the
activation barrier height and exothermicity, respectively.
Therefore, if we take as our best values the CCSD(T) results
of 10.4 and |-|\65.2 kcal/mol, respectively, our prediction would
be an activation barrier height of 9.3 kcal/mol and an
exothermicity of |-|\62.8 kcal/mol. Calculations with larger
basis sets and MP2 geometries gave 7.4 and |-|\66.2 kcal/mol,
respectively :cite:`Ford:97`. The experimental estimation
gives a lower limit to the activation barrier of 3.3 kcal/mol
:cite:`Ford:97`.

.. index::
   single: Mulliken analysis
   single: Properties; Mulliken analysis

|molcas| provides also a number of one-electron properties
which can be useful to analyze the chemical behavior of the systems.
For instance, the Mulliken population analysis is available for the
RHF, CASSCF, CASPT2, MRCI, and ACPF wave functions. Mulliken charges
are known to be strongly biased by the choice of the basis sets,
nevertheless one can restrict the analysis to the relative charge
differences during the course of the reaction to obtain a qualitative
picture. We can use, for instance, the charge distribution obtained
for the MRCI wave function, which is listed in :numref:`tab:Mq`.
Take into account that the absolute values of the charges can
vary with the change of basis set.

.. table:: Mulliken's population analysis (partial charges) for the reaction path from dimethylcarbene to propene. MRCI wave functions.
   :name: tab:Mq

   ================================== ================================== ================================== ================================== ================================== ==================================
   :math:`\ce{C{2}}`\ [#f]_           :math:`\ce{C{1}}`\ [#g]_           :math:`\ce{H{5}}`\ [#h]_           :math:`\Sigma`\ [#i]_              :math:`\ce{H{1}}+\ce{H{3}}`\ [#j]_ :math:`\ce{Me}`\ [#k]_
   ================================== ================================== ================================== ================================== ================================== ==================================
   *Dimethylcarbene*
   -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
   |-|\0.12                           |-|\0.13                           0.05                               |-|\0.20                           0.14                               0.07
   *Transition state structure*
   -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
   |-|\0.02                           |-|\0.23                           0.05                               |-|\0.20                           0.17                               0.02
   *Propene*
   -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
   |-|\0.18                           |-|\0.02                           0.05                               |-|\0.15                           0.18                               |-|\0.02
   ================================== ================================== ================================== ================================== ================================== ==================================

.. [#f] Carbon from which the hydrogen is withdrawn.
.. [#g] Central carbenoid carbon.
.. [#h] Migrating hydrogen.
.. [#i] Sum of charges for centers :math:`\ce{C{2}}`, :math:`\ce{C{1}}`, and :math:`\ce{H{5}}`.
.. [#j] Sum of charges for the remaining hydrogens attached to :math:`\ce{C{2}}`.
.. [#k] Sum of charges for the spectator methyl group.

In dimethylcarbene both the medium and terminal carbons appear equally charged.
During the migration of hydrogen :math:`\ce{H{5}}` charge flows from the hydrogen donating
carbon, :math:`\ce{C{2}}`, to the carbenoid center. For the second half of the reaction
the charge flows back to the terminal carbon from the centered carbon, probably
due to the effect of the :math:`\pi` delocalization.
