CCL: BSSE Counterpoise correction



Hi,
 Let me summarize the procedure for interaction energy calculation of a
 molecular assembly AB in the ground state.
 Geometry optimize the complex AB and the isolated monomers A & B. Perform
 the so called 'Frequency calculation' on the optimized geometries of AB, A
 and B, to confirm that all the frequencies are real. Now if you calculate
 E(AB) - E(A) - E(B), then you will get the preliminary interaction energy.
 Note that E(AB), E(A) & E(B) are the electronic energies corresponding to
 the optimized geometries of AB, A and B, respectively. Next perform
 counterpoise calculation on the optimized geometry of AB. This will give
 the correction energy due to BSSE, say E(BSSE). Now add E(BSSE) to the
 preliminary interaction energy to get the BSSE corrected interaction
 energy, i.e., E(AB) - E(A) - E(B) + E(BSSE).
 This interaction energy can further be modified by adding deformation
 correction and zero point vibrational energy correction. For that you may
 have a look at the supporting information (page S5 onwards) of the
 following article https://pubs.acs.org/doi/abs/10.1021/acsomega.8b03689
 Best wishes,
 Antarip Halder
 Research Associate
 SSCU, IISc
 On Mon, Jul 1, 2019 at 7:16 PM Lee Jones bunglinpie---googlemail.com <
 owner-chemistry__ccl.net> wrote:
 >
 > Sent to CCL by: "Lee  Jones" [bunglinpie**googlemail.com]
 > Hi
 >
 > Thanks for your reply.
 >
 > I think I have it now, but just to make sure i'm following you correctly,
 > I
 > should perform CP correction calculations on the Transition state AB* and
 > the bonded addition product AB, but would calculate the energies of the
 > individual reactants A and B in the normal way without any CP corrections?
 >
 > Is it best to perform a geometry optimisation+freq with CP correction
 > active, or should I optimise first, then perform a single point CP
 > correction on the optimised structure?  The basis set size can have an
 > effect on the geometry and frequencies so I guess it would make sense for
 > CP to be active throughout.
 >
 > Thanks
 >
 >
 > > "Antarip Halder antarip.halder:_:gmail.com"  wrote:
 > >
 > > Sent to CCL by: Antarip Halder [antarip.halder++gmail.com]
 > > --000000000000a2e42d058c6e9ce7
 > > Content-Type: text/plain; charset="UTF-8"
 > >
 > > Hi,
 > >
 > > BSSE comes into picture when you want to calculate the interaction
 energy
 > > of a molecular assembly (say XY). Interaction energy of a molecular
 > > assembly is defined as electronic energy of the complete assembly XY
 > (E_XY)
 > > minus the sum of the electronic energies of individual monomer (E_X +
 > E_Y).
 > > The problem is, to construct the wave function for XY we use more
 number
 > of
 > > basis set functions than for X or Y. Therefore, the energy difference
 > (E_XY
 > > - E_X -E_Y) gets overestimated. All the three energies should be
 > calculated
 > > using same number number of basis set functions and that is taken care
 of
 > > by the counterpoise method.
 > >
 > > Now in your case, if you want to find out the correct interaction
 energy
 > of
 > > the bio-molecular assembly AB then run CP calculation on AB to get the
 > BSSE
 > > correction (say E_BSSE). So your final interaction energy should be,
 > E_AB
 > -
 > > E_A - E_B + E_BSSE. Similarly if you are interested to find out how
 > stable
 > > your intermediate (AB)* is, then calculate its interaction energy as,
 > > E_(AB)* - E_A - E_B + E*_BSSE. Here E*_BSSE is the correction energy
 > > obtained from the counterpoise calculation performed on (AB)*.
 > >
 > > Hope this helps.
 > >
 > > Thanks,
 > > Antarip
 > >
 > > On Sat, Jun 29, 2019 at 5:01 AM Lee Jones bunglinpie[*]googlemail.com
 <
 > > owner-chemistry]~[ccl.net> wrote:
 > >
 > > >
 > > > Sent to CCL by: "Lee  Jones"
 [bunglinpie|,|googlemail.com]
 > > > Hi.  I'm after a little guidance regarding Basis Set
 Superposition
 > Error.
 > > >
 > > > I understand what BSSE is and how to perform a counterpoise
 correction
 > > > using ghost atoms, but my question is a little more fundamental.
 > > >
 > > > Considering a bimolecular addition reaction where you have
 reactants A
 > > > and B that proceed to form a single molecule AB via a transition
 state
 > > > AB*, what species do you actually perform the CP correction on?
 > > >
 > > > I read the following article which contains the following
 passage:
 > > >
 > > > https://scicomp.stackexchange.com/questions/3/what-is-counterpoise-
 > > > correction
 > > >
 > > > "This correction will depend on the geometries of the
 reactants. When
 > > > they are very far from one another, it will be very small: they
 don't
 > > > influence one another. When they are very close, this effect will
 be
 > > > small, for the same reasoning. It's the intermediate distances
 that
 > have
 > > > the largest BSSE. These are the distances at or approaching the
 > > > transition state, which serves as the bottleneck for the
 reaction. If
 > you
 > > > are not accounting for the artificial improvement near the
 transition
 > > > state, then you will get an incorrect approximation of the
 activation
 > > > energy, the energy difference between this transition state and
 the
 > > > separated-reactant limit."
 > > >
 > > >
 > > > This seems to suggest that, to a first approximation, I would
 only need
 > > > to CP correct the transition state AB* and can effectively ignore
 BSSE
 > > > for the reactants A and B at infinite distance and for the final
 > product
 > > > AB (i.e. the BSSE only has a small effect on the overall reaction
 > > > energy/enthalpy) is this correct.
 > > >
 > > >
 > > > Thanks>
 > > >
 > > >
 > >
 > > --
 > > If you think you can, you are right.
 > >
 > > --000000000000a2e42d058c6e9ce7
 > > Content-Type: text/html; charset="UTF-8"
 > > Content-Transfer-Encoding: quoted-printable
 > >
 > > <div
 dir=3D"ltr"><div>Hi,</div><div><br></div><div>BSSE
 comes into
 > picture =
 > > when you want to calculate the interaction energy of a molecular
 > assembly
 > (=
 > > say XY). Interaction energy of a molecular assembly is defined as
 > electroni=
 > > c energy of the complete assembly XY (E_XY) minus the sum of the
 > electronic=
 > >  energies of individual monomer (E_X + E_Y). The problem is, to
 > construct
 > t=
 > > he wave function for XY we use more number of basis set functions than
 > for =
 > > X or Y. Therefore, the energy difference (E_XY - E_X -E_Y) gets
 > overestimat=
 > > ed. All the three energies should be calculated using same number
 number
 > of=
 > >  basis set functions and that is taken care of by the counterpoise
 > method.<=
 > > /div><div><br></div><div>Now in your case,
 if you want to find out the
 > corr=
 > > ect interaction energy of the bio-molecular assembly AB then run CP
 > calcula=
 > > tion on AB to get the BSSE correction (say E_BSSE). So your final
 > interacti=
 > > on energy should be, E_AB - E_A - E_B + E_BSSE. Similarly if you are
 > intere=
 > > sted to find out how stable your intermediate (AB)* is, then calculate
 > its =
 > > interaction energy as, E_(AB)* - E_A - E_B + E*_BSSE. Here E*_BSSE is
 > the
 > c=
 > > orrection energy obtained from the counterpoise calculation performed
 on
 > (A=
 > > B)*.</div><div><br></div><div>Hope this
 helps.</div><div><br></div>
 > <div>Tha=
 > >
 nks,</div><div>Antarip<br></div></div><br><div
 > class=3D"gmail_quote"><div
 > d=
 > > ir=3D"ltr" class=3D"gmail_attr">On Sat, Jun 29,
 2019 at 5:01 AM Lee
 > Jones
 > b=
 > > unglinpie[*]<a href=3D"http://googlemail.com";>googlemail.com</a> &lt;<a
 > hre=
 > > f=3D"mailto:owner-chemistry]~[ccl.net";>owner-chemistry]~[ccl.net</a>&gt;
 >
 > wrote:=
 > > <br></div><blockquote class=3D"gmail_quote"
 style=3D"margin:0px 0px 0px
 > 0.8=
 > > ex;border-left:1px solid
 rgb(204,204,204);padding-left:1ex"><br>
 > > Sent to CCL by: &quot;Lee=C2=A0 Jones&quot;
 [bunglinpie|,|<a
 > href=3D"http:/=
 > > /googlemail.com" rel=3D"noreferrer"
 target=3D"_blank">googlemail.com
 > </a>]
 > <b=
 > > r>
 > > Hi.=C2=A0 I&#39;m after a little guidance regarding Basis Set
 > Superposition=
 > >  Error.<br>
 > > <br>
 > > I understand what BSSE is and how to perform a counterpoise correction
 > <br>
 > > using ghost atoms, but my question is a little more
 fundamental.<br>
 > > <br>
 > > Considering a bimolecular addition reaction where you have reactants A
 > <br>
 > > and B that proceed to form a single molecule AB via a transition state
 > <br>
 > > AB*, what species do you actually perform the CP correction
 on?<br>
 > > <br>
 > > I read the following article which contains the following
 passage:<br>
 > > <br>
 > > <a href=3D"https://scicomp.stackexchange.com/questions/3/what-is-
 > counterpoi=
 > > se-" rel=3D"noreferrer"
 > target=3D"_blank">https://scicomp.stackexchange.com=
 > > /questions/3/what-is-counterpoise-</a><br>
 > > correction<br>
 > > <br>
 > > &quot;This correction will depend on the geometries of the
 reactants.
 > When =
 > > <br>
 > > they are very far from one another, it will be very small: they
 > don&#39;t
 > <=
 > > br>
 > > influence one another. When they are very close, this effect will be
 <br>
 > > small, for the same reasoning. It&#39;s the intermediate distances
 that
 > hav=
 > > e <br>
 > > the largest BSSE. These are the distances at or approaching the
 <br>
 > > transition state, which serves as the bottleneck for the reaction. If
 > you
 > <=
 > > br>
 > > are not accounting for the artificial improvement near the transition
 > <br>
 > > state, then you will get an incorrect approximation of the activation
 > <br>
 > > energy, the energy difference between this transition state and the
 <br>
 > > separated-reactant limit.&quot;<br>
 > > <br>
 > > <br>
 > > This seems to suggest that, to a first approximation, I would only
 need
 > <br=
 > > >
 > > to CP correct the transition state AB* and can effectively ignore BSSE
 > <br>
 > > for the reactants A and B at infinite distance and for the final
 product
 > <b=
 > > r>
 > > AB (i.e. the BSSE only has a small effect on the overall reaction
 <br>
 > > energy/enthalpy) is this correct.<br>
 > > <br>
 > > <br>
 > > Thanks<br>
 > > <br>
 > > <br>
 > > <br>
 > > -=3D This is automatically added to each message by the mailing script
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 > > </blockquote></div><br
 clear=3D"all"><br>-- <br><div dir=3D"ltr"
 > class=3D"g=
 > > mail_signature">If you think you can, you are
 right.<br></div>
 > >
 > > --000000000000a2e42d058c6e9ce7-->
 >
 >
 --
 If you think you can, you are right.