[ADF-LIST] FWD：FWD：中间旋转的EDA（S = 1）Fe-Oxocomplex
Fedor Goumans. 在Scm.com的Goumans1月18日星期一10:01:16 CET 2016
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-------- 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 _______________________________________________ ADFlist mailing list ADFlist at scm.com http://lists.tofoba.com/mailman/listinfo/adflist -- dr Mariusz Mitoraj Department of Theoretical Chemistry Faculty of Chemistry, Jagiellonian University 30-060 Krakow, Ingardena 3 Poland -------------- next part -------------- An HTML attachment was scrubbed... URL: <//lists.tofoba.com/pipermail/adflist/attachments/20160118/d687d045/attachment.html>
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