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Davidson size-consistency corrections for truncated CI wave functions
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Background
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A serious deficiency of truncated CI expansions, including the most popular ones, namely (multi-reference; MR)CI-SD is
the lack of size-consistency; i.e., the energy of the system does not scale properly with the system size. Besides
corrections to the CI equations which will improve the energy and the wave function, *a posteriori* corrections (most often
referred to as *Davidson-type* corrections or *+Q*) to the energy have become quite popular. A comprehensive overview on this topic has been
given recently in a `review paper on multiconfigurational and multirefernce methods
`_. Starting with Dirac14 we have implemented a number of different flavors of the latter *a posteriori* corrections to the
energy for the modules KRCI and LUCITA. The nomenclature and detailed equations for each correction is explained in great
detail in the above review article (see chapter 2.1.3.1).
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Example: Water
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Following the example for water in the `review article `_ we need to run two
calculations. Although it's possible to do it in one step we will split the task in two.
Step 1: Get reference wave function and configuration(s)
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We first start with a multiconfigurational SCF calculation for water with a CAS(4,4) space using a cc-pVDZ basis set.
This will yield a suitable reference wave function for the subsequent CI. The MCSCF module will in addition automatically create a file named **refvec.luci** which
contains the reference configurations needed later for the *+Q* corrections. Our CASSCF input ``scf-casscf.inp`` is
.. literalinclude:: scf-casscf.inp
The molecular structure is located in ``h2o.xyz``
.. literalinclude:: h2o.xyz
Suppose that we have run the CASSCF calculation using::
pam --inp=scf-casscf.inp --mol=h2o.xyz --outkrmc --get="refvec.luci"
where we keep the MCSCF coefficients (in KRMCSCF) and the reference vectors stored in refvec.luci we are now in position
to proceed to Step 2.
Step 2: Run the MRCISD calculation and compute the +Q corrections
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In the second step we now run a MRCISD calculation using the reference wave function coefficients from the previous step
as starting point and compute the *+Q* corrections to the MRCISD energy.
Using the same molecular input structure we run the MRCISD+Q calculation using the input file ``krci-q.inp``
.. literalinclude:: krci-q.inp
with the following start command::
pam --inp=scf-casscf.inp --mol=h2o.xyz --inkrmc --put="refvec.luci"
We will find a summary of different *+Q* corrections printed at the end of the output:
.. literalinclude:: summary_q.txt
where a detailed account of the general *performance* of the different *+Q* corrections (and which other QC programs have
implemented which *+Q* correction by default) is given in chapter 2.1.3.1 of the above given review article. The
equations references given in the output match the equation labels given in chapter 2.1.3.1. We strongly recommend the
interested user to carefully read this chapter 2.1.3.1.