[ADF-LIST] FWD:FWD:中间旋转的EDA(S = 1)Fe-Oxocomplex

Fedor Goumans. 在Scm.com的Goumans
1月18日星期一10:01:16 CET 2016


-------- Forwarded Message --------
Subject: 	Fwd:  [ADF-LIST]中间旋转的EDA(S = 1)Fe-Oxo复合物 
Date: 	Mon, 18 Jan 2016 08:33:51 +0100
From: 	mitoraj <mitoraj at chemia.uj.edu.pl>
To: 	johannes.straub at aci.uni-heidelberg.de, Fedor Goumans < 在Scm.com的Goumans >



Dear Johannes,

as you have noticed the ADF uses restricted fragments so far and
unfortunately
fragoccupations keyword doesn't allow you for moving one electron from
one SFO to another one,
in other words fragment calculation with specification:

PI 2 2 1 1

really means that each of the two last SFO's contain hafl-alpha and
half-beta
electrons and fragoccupations allows to to change the overall spin
only
within these fragment SFO's (by sth like that 1 1 1 1//1 1 0 0) to make
them "fully-one-alpha" (or beta),
you can not start from:

PI 2 2 2 in fragment calculations

and make it: PI 2 2 1 1 using fragoccupations,

the only way is first to do, for example
PI 2 2 1 1 in fragment calculations, and then apply fragoccupations in
final calculations,


best,


Mariusz







-------- Wiadomość oryginalna --------
Temat:  [ADF-LIST]中间旋转的EDA(S = 1)Fe-Oxo复合物 
Data: 2016-01-15 15:07
Od: Johannes Straub <johannes.straub at aci.uni-heidelberg.de>
Do: adflist at scm.com
Odpowiedź do: ADF discussion list <adflist at scm.com>

Dear ADF community,

the last couple of days or weeks I was trying to do an EDA of an
intermediate spin (S=1) Fe(IV)-oxo bispidine (pentadentate ligand with
5
N donors) complex.
So the charge and excess of alpha-spin electrons would be both 2.
Overall symmetry is C1.

Now I'm interested in the interaction of the [Fe=O]2+ fragment (charge
+2, open shell, S=1) with the ligand (neutral, closed shell).
First I tried to use an unrestricted fragment (from an UNRESTRICTED,
charge 2 2 calculation), but in the EDA calculation I got an error
message "ADF EXIT CALLED UNRESTRICTED FRAGMENT". So I more carefully
read the manual part about fragoccupations, and if I understand
correctly, I cannot use unrestricted fragments for the EDA calculation.
Furthermore, it's written that the occupation of an orbital of a
fragment calculation must be the same as in the calculation where I put
the fragments together.
Just to put this in a simple question: Is it correct, that I cannot
have
e.g. a fully occupied dz2 orbital in the fragment calculation on the
one
hand and take one electron out and put it in a so far empty e.g. dxy
orbital in the unrestricted calculation, where I put together the two
fragments on the other hand? Becaue this would mean, that the
occupation
of this dz2 orbital would be 2 in the fragment calculation and only 1
in
the following calculation?
I'm asking this, because, if I try to do exaclty this, I always get an
error "INCONSISTENT FRAGMENT OCCUPATIONS". Or is there a different
reason?

So my problem still is, that I have an Fe(IV)=0 fragment with an
occupation of the d-orbitals, which would be correct for a this kind of
a linear molecule; the d-orbital ordering would be two degenerate
orbitals (x2-y2, xy), another two degenerate orbitals (xz, yz) and the
z2 orbital hightest in energy. But if I now try to put this fragment
into my ligand (or if I put together the two fragments in an EDA
calculation), the ligand field would be different and in this case I'd
get a d-orbital ordering like xy (2e-) -> xz, yz (degenerate, both 1e-)
-> x2-y2 (empty) and dz2 (empty) highest in energy. So the occupations
of the d-orbitals significantly changes from the fragment part to the
whole EDA calculation.

How could I perform an EDA calculations with the two fragments
mentioned?
In the following part, I have attached the input of one of my tries.

CALCULATION OF Fe=O, fragment 1, which should make sure, that the
irreps
are occupied as they should be later on.
#! /bin/sh

# ==============================
# The Molecule
# ==============================

"$ADFBIN/adf" <<eor
TITLE Region_1 fragment

ATOMS
1 Fe       1.182653000000      -0.250196000000       0.897069000000
R=1.50
2 O       1.998176000000      -0.470406000000       2.287578000000
R=1.40
END

GUIBONDS
1 1 2 3
END

SYMMETRY C(LIN)

CHARGE 2.0 0

OCCUPATIONS
     SIGMA 16
     PI 14
     DELTA 2
END

BASIS
type TZP
core None
createoutput None
END

XC
Hybrid B3LYP
END

SAVE  TAPE21 TAPE13

BeckeGrid
     Quality Good
End

STOFIT

NOPRINT LOGFILE



CALCULATION OF THE WHOLE MOLECULE, EDA

#! /bin/sh

# dependency: {} test5.Region_1.t21
# dependency: {} test5.Region_2.t21
# ==============================
# The Molecule
# ==============================

"$ADFBIN/adf" <<eor
!!ATOMS and GUIBONDS left out!! for a better overview, of course there
are in the input file.

SYMMETRY NOSYM

CHARGE 2.0 2.0

UNRESTRICTED

SCRF
     RADIUS Fe 1.50
     RADIUS N 1.55
     RADIUS C 1.70
     RADIUS H 1.20
     RADIUS O 1.40
     EPSSOL 37.5
     SOLRAD 2.002072539
     MEADGRID ON_GEOM_CENT 43 1.0
     MEADGRID ON_GEOM_CENT 105 0.15
END

BASIS
type TZP
core None
createoutput None
END

XC
Hybrid B3LYP
END

FRAGOCCUPATIONS
     Region_1
     SIGMA 8 // 8
     PI 6 1 1 // 6 0 0
     DELTA 1 // 1
     subend
end

OCCUPATIONS
     A 153 // 151
END

Fragments
     Region_1 test5.Region_1.t21
     Region_2 test5.Region_2.t21
end

ETSNOCV
PRINT ETSLOWDIN-UNRESTRICTED

SAVE  TAPE21 TAPE13

BeckeGrid
     Quality Good
End

STOFIT

NOPRINT LOGFILE

eor


Is this, in principle, the right way of doing this calculation? Is
there
any severe mistake?
I hope you can help me out with this one!

Best wishes

Johannes Straub

-- 
Johannes Straub
PhD Student, Comba group
University of Heidelberg
Im Neuenheimer Feld 270
69120 Heidelberg
johannes.straub at aci.uni-heidelberg.de
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-- 
dr Mariusz Mitoraj
Department of Theoretical Chemistry
Faculty of Chemistry, Jagiellonian University
30-060 Krakow, Ingardena 3
Poland



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