19.8 Basis set extrapolation

`EXTRAPOLATE,BASIS= basislist,options`

where basislist is a list of at least two basis sets separated by colons,
e.g. AVTZ:AVQZ:AV5Z. Some extrapolation types need three or more basis sets, others only
two. The default is to use extrapolation of the correlation energies,
and in this case two subsequent basis sets and the corresponding energies are needed.
The default is not to extrapolate the reference (HF) energies; the value
obtained with the largest basis set is taken as reference energy for the CBS estimate.
However, extrapolation of the reference is also possible by specifying the `METHOD_R` option.

The simplest way to perform extraplations for standard methods like MP2 or CCSD(T) is to use, e.g.

***,H2O memory,32,m gthresh,energy=1.d-8 r = 0.9572 ang, theta = 104.52 geometry={O; H1,O,r; H2,O,r,H1,theta} basis=avtz hf ccsd(t) extrapolate,basis=avqz:av5z table,basissets,energr,energy-energr,energy head,basis,ehf,ecorr,etot

This will perform the first calculation with AVTZ basis, and then compute the estimated basis set limit using the AVQZ and AV5Z basis sets. The correlation energy obtained in the calculation that is performed immediately before the extrapolate command will be extrapolated (in this case the CCSD(T) energy), and the necessary sequence of calculations [here HF;CCSD(T)] will be automatically carried out. Unless otherwise specified (see below), the Hartree-Fock energy is taken from the largest basis set and not extrapolated.

The resulting energies are returned in variables ENERGR (reference energies), ENERGY (total energies), and ENERGD (Davidson corrected energy if available); the corresponding basis sets are returned in variable BASISSETS. The results can be printed, e.g., in a table as shown above, or used otherwise. The above input produces the table

BASIS EHF ECORR ETOT AVQZ -76.06600082 -0.29758099 -76.36358181 AV5Z -76.06732050 -0.30297495 -76.37029545 CBS -76.06732050 -0.30863418 -76.37595468

The extrapolated total energy is also returned in variable ECBS (ECBSD for Davidson corrected energy if available).

In order to extrapolate the HF energy as well (for example using Karton-Martin extrapolation), one can modify the input as follows:

`extrapolate,basis=avqz:av5z,method_r=km`

This yields

BASIS EREF ECORR ETOT AVQZ -76.06600082 -0.29758099 -76.36358181 AV5Z -76.06732050 -0.30297495 -76.37029545 CBS -76.06754138 -0.30863418 -76.37617556

Alternatively, one can do the energy calculations manually and pass the energies to be extrapolated to extrapolate via variables. This is more flexible and allows to carry out different extrapolations with the same energies.

For example:

***,H2O memory,32,m gthresh,energy=1.d-8 !energy convergence threshold r = 0.9572 ang, theta = 104.52 geometry={O; H1,O,r; H2,O,r,H1,theta} basis=vqz hf ccsd(t) eref(1)=energr !VQZ reference (HF) energy etot(1)=energy !VQZ ccsd(t) total energy basis=v5z hf ccsd(t) eref(2)=energr !V5Z reference (HF) energy etot(2)=energy !V5Z ccsd(t) total energy text,extrapolate total energy: extrapolate,basis=vqz:v5z,etot=etot text,extrapolate correlation energy only: extrapolate,basis=vqz:v5z,etot=etot,eref=eref text,extrapolate reference and correlation energies separately: extrapolate,basis=vqz:v5z,etot=etot,eref=eref,method_r=km

This yields

For extrapolation of the total energy:

BASIS ENERGY VQZ -76.35979334 V5Z -76.36904020 CBS -76.37874183

For extrapolation of the correlation energy only:

BASIS EREF ECORR ETOT VQZ -76.06483534 -0.29495800 -76.35979334 V5Z -76.06709083 -0.30194937 -76.36904020 CBS -76.06709083 -0.30928458 -76.37637541

For separate extrapolation of reference and correlation energies:

BASIS EREF ECORR ETOT VQZ -76.06483534 -0.29495800 -76.35979334 V5Z -76.06709083 -0.30194937 -76.36904020 CBS -76.06746834 -0.30928458 -76.37675292

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molpro@molpro.net 2018-06-21