CCL:G: Help with DFT convergence failure for Fe2CO2 in Gaussian software

[Cheng Fei Phung <feiphung a hotmail.com>]

Hi,

the following is from chatGPT, what do you guys think ?

When using the 6-311G basis set, it is common to add diffuse functions to improve the description of electron correlation and dispersion interactions. One commonly used set of diffuse functions is the "polarization-consistent basis set" (pcS-n, where n is an integer), which adds diffuse functions to the valence and polarization sets in a consistent way.

For Fe2+ ferrous ion, a suitable choice of diffuse functions would depend on the level of accuracy required and the size of the system. As a starting point, you could consider adding diffuse functions up to the pcS-4 level, which would add 4 sets of diffuse functions to the 6-311G basis set.

To specify the pcS-4 basis set in Gaussian, you can use the following basis set specification:

```

# opt umn15l/6-311++g(d,p) scrf=(solvent=water) geom=connectivity

Fe2CO2_OPT

2 3

 Fe                 2.74538330    8.28679554    5.00000000

 O                  4.55208397    8.06717607    5.00000000

 C                  5.30819317    9.07309328    5.00000000

 O                  5.97838127    9.96470142    5.00000000

 1 2 1.0

 2 3 2.0

 3 4 3.0

 4

Fe S 4

6-311G(d,p)  Fe 4,4,4,4,4,4

****

C S 1

6-311G(d,p)  C 3,3,3,3,3,3

****

O S 2

6-311G(d,p)  O 3,3,3,3,3,3

****

```

In this input file, the "S" keyword specifies that diffuse functions should be added to the basis set, and the "4" after "Fe S" indicates that 4 sets of diffuse functions should be added to the iron atom. The same format is used for the carbon and oxygen atoms.

It is also worth noting that the use of solvent models, such as the SCRF model with water as the solvent, can further improve the accuracy of calculations by including the effects of solvation. However, the choice of solvent model and the level of theory used for the calculation of solvent effects can also affect the accuracy of the results.

---

From: owner-chemistry+feiphung==hotmail.com{}ccl.net <owner-chemistry+feiphung==hotmail.com{}ccl.net> on behalf of David Shobe shobedavid]^[gmail.com <owner-chemistry{}ccl.net>
Sent: Wednesday, March 1, 2023 7:53 PM
To: Phung, Cheng Fei <feiphung{}hotmail.com>
Subject: CCL:G: Help with DFT convergence failure for Fe2CO2 in Gaussian software

 

Dear Cheng Fei Phung --

Isolated Fe^2+ is a quintuplet in the ground state. The coordination with the CO2 molecule may change it to a different electronic state, most likely to a triplet. 

The charge and multiplicity are specified by replacing the "0 1" line with "2 5" for the quintuplet or "2 3" for the triplet. The "++" in GaussView is a red herring (if you don't know this _expression_, it refers to a misleading clue), as the "++" refers to diffuse functions in the basis set. 

Good luck! Calculations of transition metals are difficult. I should warn you that even if you get a converged SCF, it might not be the correct electronic state. Take a look at the manual under the keywords SCF and stable for more information.

--David Shobe 

On Wed, Mar 1, 2023, 2:48 AM Cheng Fei Phung feiphung-*-hotmail.com <owner-chemistry::ccl.net> wrote:

Hi,

Since my messages contains the image and is longer than a limit for general distribution,

the CCL Admin saved my message under

http://www.ccl.net/large_message/2023-02-28-LongMessage.html

so please open this link to read my response

Note that I am doing Fe2+ ferrous ion for MOF carbon capture

What do you guys think about the following xtb result from https://calcus.cloud/ ?

step_000_DFT.Geometrical_Optimisation_Result.xyz :

4

 energy: -13.349149310898 gnorm: 0.000502022323 xtb: 6.5.1 (579679a)

Fe           2.73292919494009        7.81690557181600        4.99999999991402

O            4.23822629938734        8.62616541285678        4.99975863372067

C            5.28034049639189        9.19333556707946        5.00051367720569

O            6.33254571928068        9.75535975824776        4.99972768915961

Regards,

Cheng Fei  Phung

---

From: owner-chemistry+feiphung==hotmail.com_-_ccl.net <owner-chemistry+feiphung==hotmail.com_-_ccl.net> on behalf of Igors Mihailovs igorsm_._cfi.lu.lv <owner-chemistry_-_ccl.net>
Sent: Sunday, February 26, 2023 10:50 PM
To: Phung, Cheng Fei <feiphung_-_hotmail.com>
Subject: CCL:G: Re: CCL:G: Help with DFT convergence failure for Fe2CO2 in Gaussian software

 

Dear Cheng Fei  Phung,

I would use something like MN15 or MN15L, and a basis set with at least some polarization (6-311G(d,p), for example). Especially if I had to perform something like a token computation in order to get someone's experimental results published.

Trying to converge B3LYP for a transition metal compound may take more time than the options described above...

Best regards,
Igors Mihailovs
former employee at ISSP UL

On February 25, 2023 12:09:02 PM GMT+02:00, "Cheng Fei Phung feiphung=-=hotmail.com" <owner-chemistry^-^ccl.net> wrote:

Sent to CCL by: "Cheng Fei  Phung" [feiphung{:}hotmail.com]
With the following gaussian16 gjf input
 file, I got some convergence failure issues.

Could anyone help
 ?


Gaussian input gjf file

```
%chk=step_000_DFT.chk
#
 opt b3lyp/6-31g geom=connectivity

Fe2CO2_OPT

0 1
 Fe
 2.74538330    8.28679554    5.00000000
 O                  4.55208397
 8.06717607    5.00000000
 C                  5.30819317    9.07309328
 5.00000000
 O                  5.97838127    9.96470142    5.00000000


 1 2 1.0
 2 3 2.0
 3 4 3.0
 4
```


Gaussian log
 file

```
 %chk=step_000_DFT.chk
 # opt b3lyp/6-31g
 geom=connectivity
 1/18=20,19=15,26=3,38=1,57=2/1,3;

 2/9=110,12=2,17=6,18=5,40=1/2;

 3/5=1,6=6,11=2,25=1,30=1,71=1,74=-5/1,2,3;
 4//1;
 5/5=2,38=5/2;

 6/7=2,8=2,9=2,10=2,28=1/1;
 7//1,2,3,16;
 1/18=20,19=15,26=3/3(2);

 2/9=110/2;
 99//99;
 2/9=110/2;

 3/5=1,6=6,11=2,25=1,30=1,71=1,74=-5/1,2,3;
 4/5=5,16=3,69=1/1;

 5/5=2,38=5/2;
 7//1,2,3,16;
 1/18=20,19=15,26=3/3(-5);
 2/9=110/2;

 6/7=2,8=2,9=2,10=2,19=2,28=1/1;
 99/9=1/99;
 Fe2CO2_OPT
 Symbolic
 Z-matrix:
 Charge =  0 Multiplicity = 1
 Fe                    2.74538
 8.2868    5. 
 O                     4.55208   8.06718   5. 
 C
 5.30819   9.07309   5. 
 O                     5.97838   9.9647    5. 

 


 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad

 Berny optimization.
 Initialization pass.
                           !
 Initial Parameters    !
                           ! (Angstroms and Degrees)
 !
 --------------------------
 --------------------------
 ! Name  Definition              Value
 Derivative Info.                !
 ! R1    R(1,2)                  1.82
 estimate D2E/DX2                !
 ! R2    R(2,3)                  1.2584
 estimate D2E/DX2                !
 ! R3    R(3,4)                  1.1154
 estimate D2E/DX2                !
 ! A1    A(1,2,3)              120.0
 estimate D2E/DX2                !
 ! A2    L(2,3,4,1,-1)         180.0
 estimate D2E/DX2                !
 ! A3    L(2,3,4,1,-2)         180.0
 estimate D2E/DX2                !
 Trust Radius=3.00D-01 FncErr=1.00D-07
 GrdErr=1.00D-06 EigMax=2.50D+02 EigMin=1.00D-04
 Number of steps in this run=
 20 maximum allowed number of steps=    100.

 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad


 Input orientation:                          
 Center     Atomic      Atomic
 Coordinates (Angstroms)
 Number     Number       Type             X
 Y           Z
      1         26           0        2.745383    8.286796
 5.000000
      2          8           0        4.552084    8.067176
 5.000000
      3          6           0        5.308193    9.073093
 5.000000
      4          8           0        5.978381    9.964701
 5.000000
                    Distance matrix (angstroms):

 1          2          3          4
     1  Fe   0.000000
     2  O
 1.820000   0.000000
     3  C    2.680720   1.258400   0.000000
     4  O
 3.642478   2.373800   1.115400   0.000000
 Stoichiometry    CFeO2

 Framework group  CS[SG(CFeO2)]
 Deg. of freedom     5
 Full point group
 CS      NOp   2
 Largest Abelian subgroup         CS      NOp   2
 Largest
 concise Abelian subgroup C1      NOp   1
                         Standard
 orientation:                         
 Center     Atomic      Atomic
 Coordinates (Angstroms)
 Number     Number       Type             X
 Y           Z
      1         26           0       -1.018287   -0.652610
 -0.000000
      2          8           0       -0.000000    0.855864
 0.000000
      3          6           0        1.255302    0.767619
 0.000000
      4          8           0        2.367956    0.689403
 0.000000
 Rotational constants (GHZ):          37.1744583           2.4897380
 2.3334561
 Standard basis: 6-31G (6D, 7F)
 There are    42 symmetry
 adapted cartesian basis functions of A'  symmetry.
 There are    14 symmetry
 adapted cartesian basis functions of A"  symmetry.
 There are    42
 symmetry adapted basis functions of A'  symmetry.
 There are    14 symmetry
 adapted basis functions of A"  symmetry.
    56 basis functions,   160
 primitive gaussians,    56 cartesian basis functions
    24 alpha electrons
 24 beta electrons
       nuclear repulsion energy       178.7145642873
 Hartrees.
 NAtoms=    4 NActive=    4 NUniq=    4 SFac= 1.00D+00 NAtFMM=   60
 NAOKFM=F Big=F
 Integral buffers will be    131072 words long.
 Raffenetti
 2 integral format.
 Two-electron integral symmetry is turned on.

 One-electron integrals computed using PRISM.
 NBasis=    56 RedAO= T EigKep=
 1.76D-03  NBF=    42    14
 NBsUse=    56 1.00D-06 EigRej= -1.00D+00 NBFU=
 42    14
 ExpMin= 4.11D-02 ExpMax= 6.11D+04 ExpMxC= 9.18D+03 IAcc=3 IRadAn=
 5 AccDes= 0.00D+00
 Harris functional with IExCor=  402 and IRadAn=       5
 diagonalized for initial guess.
 HarFok:  IExCor=  402 AccDes= 0.00D+00
 IRadAn=         5 IDoV= 1 UseB2=F ITyADJ=14
 ICtDFT=  3500011 ScaDFX=
 1.000000  1.000000  1.000000  1.000000
 FoFCou: FMM=F IPFlag=           0
 FMFlag=      100000 FMFlg1=           0
         NFxFlg=           0 DoJE=T
 BraDBF=F KetDBF=T FulRan=T
         wScrn=  0.000000 ICntrl=       500 IOpCl=
 0 I1Cent=   200000004 NGrid=           0
         NMat0=    1 NMatS0=      1
 NMatT0=    0 NMatD0=    1 NMtDS0=    0 NMtDT0=    0
 Petite list used in
 FoFCou.
 Initial guess orbital symmetries:
       Occupied  (A') (A') (A')
 (A') (A") (A') (A') (A') (A') (A')
                 (A') (A") (A')
 (A') (A') (A') (A') (A") (A') (A")
                 (A') (A')
 (A") (A')
       Virtual   (A") (A') (A') (A") (A') (A")
 (A') (A') (A') (A')
                 (A") (A') (A') (A") (A') (A')
 (A') (A") (A') (A')
                 (A') (A") (A') (A') (A')
 (A") (A") (A') (A') (A')
                 (A') (A')
 The
 electronic state of the initial guess is 1-A'.
 Keep R1 ints in memory in
 symmetry-blocked form, NReq=2159799.
 Requested convergence on RMS density
 matrix=1.00D-08 within 128 cycles.
 Requested convergence on MAX density
 matrix=1.00D-06.
 Requested convergence on             energy=1.00D-06.

 No special actions if energy rises.
 EnCoef did     3 forward-backward
 iterations
 EnCoef did   100 forward-backward iterations
 EnCoef did     2
 forward-backward iterations
 EnCoef did     2 forward-backward iterations

 SCF Done:  E(RB3LYP) =  -1451.84990065     A.U. after   22 cycles

 NFock= 22  Conv=0.66D-08     -V/T= 2.0016


 **********************************************************************


 Population analysis using the SCF Density.


 **********************************************************************


 Orbital symmetries:
       Occupied  (A') (A') (A') (A') (A") (A') (A')
 (A') (A') (A')
                 (A") (A') (A') (A') (A') (A') (A")
 (A') (A') (A")
                 (A') (A') (A") (A')

 Virtual   (A") (A') (A") (A') (A') (A") (A') (A') (A') (A')

 (A") (A') (A') (A") (A') (A') (A') (A") (A') (A')

 (A') (A") (A') (A') (A') (A") (A') (A") (A') (A')

 (A') (A')
 The electronic state is 1-A'.
 Alpha  occ. eigenvalues --
 -256.04016 -29.99951 -25.87326 -25.85859 -25.85805
 Alpha  occ. eigenvalues
 --  -19.31120 -19.28742 -10.45249  -3.41064  -2.20510
 Alpha  occ.
 eigenvalues --   -2.17421  -2.16694  -1.26882  -1.17261  -0.64217
 Alpha
 occ. eigenvalues --   -0.58881  -0.57965  -0.57594  -0.44473  -0.43175
 Alpha
 occ. eigenvalues --   -0.22416  -0.22137  -0.20382  -0.15336
 Alpha virt.
 eigenvalues --   -0.07558  -0.07420  -0.03518  -0.03067  -0.02764
 Alpha
 virt. eigenvalues --   -0.00807   0.00082   0.10567   0.12952   0.29804

 Alpha virt. eigenvalues --    0.31948   0.36712   0.41870   0.45104
 0.54770
 Alpha virt. eigenvalues --    0.63606   0.74556   0.85137   0.88355
 0.92857
 Alpha virt. eigenvalues --    0.96917   1.00808   1.01595   1.25495
 1.50958
 Alpha virt. eigenvalues --    1.51252   1.55992   1.59723   1.70732
 1.86833
 Alpha virt. eigenvalues --    2.01356  20.37339

 Condensed to atoms (all electrons):
               1          2          3
 4
     1  Fe  26.065938  -0.058002   0.083106  -0.030239
     2  O
 -0.058002   8.304619   0.168196   0.010116
     3  C    0.083106   0.168196
 4.724609   0.417125
     4  O   -0.030239   0.010116   0.417125
 7.724230
 Mulliken charges:
               1
     1  Fe  -0.060803

 2  O   -0.424929
     3  C    0.606964
     4  O   -0.121232
 Sum of
 Mulliken charges =  -0.00000
 Mulliken charges with hydrogens summed into
 heavy atoms:
               1
     1  Fe  -0.060803
     2  O
 -0.424929
     3  C    0.606964
     4  O   -0.121232
 Electronic
 spatial extent (au):  <R**2>=            453.0609
 Charge=
 -0.0000 electrons
 Dipole moment (field-independent basis, Debye):
    X=
 1.6708    Y=              1.8514    Z=             -0.0000  Tot=
 2.4938
 Quadrupole moment (field-independent basis, Debye-Ang):
   XX=
 -35.0872   YY=            -34.7815   ZZ=            -32.5686
   XY=
 0.8912   XZ=              0.0000   YZ=              0.0000
 Traceless
 Quadrupole moment (field-independent basis, Debye-Ang):
   XX=
 -0.9415   YY=             -0.6357   ZZ=              1.5772
   XY=
 0.8912   XZ=              0.0000   YZ=              0.0000
 Octapole moment
 (field-independent basis, Debye-Ang**2):
  XXX=             -8.4875  YYY=
 8.6001  ZZZ=             -0.0000  XYY=              3.5470
  XXY=
 1.7153  XXZ=              0.0000  XZZ=              0.7336  YZZ=
 1.9407
  YYZ=             -0.0000  XYZ=             -0.0000
 Hexadecapole
 moment (field-independent basis, Debye-Ang**3):
 XXXX=           -415.5041
 YYYY=           -171.1039 ZZZZ=            -55.1637 XXXY=
 -84.4690
 XXXZ=              0.0000 YYYX=            -75.7822 YYYZ=
 0.0000 ZZZX=              0.0000
 ZZZY=              0.0000 XXYY=
 -90.7121 XXZZ=            -70.9019 YYZZ=            -36.9432
 XXYZ=
 0.0000 YYXZ=              0.0000 ZZXY=            -24.7602
 N-N=
 1.787145642873D+02 E-N=-3.807626875025D+03  KE= 1.449497603530D+03
 Symmetry
 A'   KE= 1.287179877057D+03
 Symmetry A"   KE= 1.623177264732D+02

 Calling FoFJK, ICntrl=      2127 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1
 NMatS=1 NMatT=0.
 ***** Axes restored to original set *****
 Center
 Atomic                   Forces (Hartrees/Bohr)
 Number     Number
 X              Y              Z
      1       26          -0.048820174
 0.005157682    0.000000000
      2        8           0.068584660
 0.015861998    0.000000000
      3        6          -0.104728901
 -0.126023309    0.000000000
      4        8           0.084964415
 0.105003629   -0.000000000
 Cartesian Forces:  Max     0.126023309 RMS
 0.066118707


 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad

 Berny optimization.
 FormGI is forming the generalized inverse of G from
 B-inverse, IUseBI=4.
 Internal  Forces:  Max     0.134986320 RMS
 0.059949734
 Search for a local minimum.
 Step number   1 out of a maximum
 of   20
 All quantities printed in internal units
 (Hartrees-Bohrs-Radians)
 Mixed Optimization -- RFO/linear search
 Second
 derivative matrix not updated -- first step.
 The second derivative
 matrix:
                          R1        R2        R3        A1
 A2
           R1           0.22791
           R2           0.00000
 0.80209
           R3           0.00000   0.00000   1.62060
           A1
 0.00000   0.00000   0.00000   0.25000
           A2           0.00000
 0.00000   0.00000   0.00000   0.05456
           A3           0.00000
 0.00000   0.00000   0.00000   0.00000
                          A3

 A3           0.05456
 ITU=  0
     Eigenvalues ---    0.05456   0.05456
 0.22791   0.25000   0.80209
     Eigenvalues ---    1.62060
 RFO step:
 Lambda=-2.30438557D-02 EMin= 5.45649275D-02
 Linear search not attempted --
 first point.
 Iteration  1 RMS(Cart)=  0.10911805 RMS(Int)=  0.00403264

 Iteration  2 RMS(Cart)=  0.00524126 RMS(Int)=  0.00001569
 Iteration  3
 RMS(Cart)=  0.00001737 RMS(Int)=  0.00000000
 Iteration  4 RMS(Cart)=
 0.00000000 RMS(Int)=  0.00000000
 ClnCor:  largest displacement from
 symmetrization is 2.67D-10 for atom     3.
 Variable       Old X    -DE/DX
 Delta X   Delta X   Delta X     New X

 (Linear)    (Quad)   (Total)
    R1        3.43930   0.04909   0.00000
 0.19560   0.19560   3.63490
    R2        2.37803  -0.02868   0.00000
 -0.03476  -0.03476   2.34327
    R3        2.10780   0.13499   0.00000
 0.08213   0.08213   2.18993
    A1        2.09440   0.00265   0.00000
 0.00969   0.00969   2.10408
    A2        3.14159   0.01018   0.00000
 0.13112   0.13112   3.27271
    A3        3.14159   0.00000   0.00000
 0.00000   0.00000   3.14159
         Item               Value     Threshold
 Converged?
 Maximum Force            0.134986     0.000450     NO 
 RMS
 Force            0.059950     0.000300     NO 
 Maximum Displacement
 0.164913     0.001800     NO 
 RMS     Displacement     0.111408     0.001200
 NO 
 Predicted change in Energy=-1.225354D-02

 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad


 Input orientation:                          
 Center     Atomic      Atomic
 Coordinates (Angstroms)
 Number     Number       Type             X
 Y           Z
      1         26           0        2.658115    8.232499
 5.000000
      2          8           0        4.576263    8.089032
 5.000000
      3          6           0        5.284531    9.106861
 5.000000
      4          8           0        6.065132    9.963375
 5.000000
                    Distance matrix (angstroms):

 1          2          3          4
     1  Fe   0.000000
     2  O
 1.923506   0.000000
     3  C    2.768135   1.240008   0.000000
     4  O
 3.821478   2.393719   1.158859   0.000000
 Stoichiometry    CFeO2

 Framework group  CS[SG(CFeO2)]
 Deg. of freedom     5
 Full point group
 CS      NOp   2
 Largest Abelian subgroup         CS      NOp   2
 Largest
 concise Abelian subgroup C1      NOp   1
                         Standard
 orientation:                         
 Center     Atomic      Atomic
 Coordinates (Angstroms)
 Number     Number       Type             X
 Y           Z
      1         26           0       -1.022093   -0.757193
 -0.000000
      2          8           0        0.000000    0.872286
 0.000000
      3          6           0        1.239558    0.838897
 0.000000
      4          8           0        2.392133    0.959419
 0.000000
 Rotational constants (GHZ):          40.3135828           2.2660782
 2.1454781
 Standard basis: 6-31G (6D, 7F)
 There are    42 symmetry
 adapted cartesian basis functions of A'  symmetry.
 There are    14 symmetry
 adapted cartesian basis functions of A"  symmetry.
 There are    42
 symmetry adapted basis functions of A'  symmetry.
 There are    14 symmetry
 adapted basis functions of A"  symmetry.
    56 basis functions,   160
 primitive gaussians,    56 cartesian basis functions
    24 alpha electrons
 24 beta electrons
       nuclear repulsion energy       172.3989508234
 Hartrees.
 NAtoms=    4 NActive=    4 NUniq=    4 SFac= 1.00D+00 NAtFMM=   60
 NAOKFM=F Big=F
 Integral buffers will be    131072 words long.
 Raffenetti
 2 integral format.
 Two-electron integral symmetry is turned on.

 One-electron integrals computed using PRISM.
 NBasis=    56 RedAO= T EigKep=
 1.76D-03  NBF=    42    14
 NBsUse=    56 1.00D-06 EigRej= -1.00D+00 NBFU=
 42    14
 Initial guess from the checkpoint file:
 "step_000_DFT.chk"
 B after Tr=     0.000000    0.000000
 -0.000000
         Rot=    0.999288   -0.000000   -0.000000   -0.037733 Ang=
 -4.32 deg.
 Initial guess orbital symmetries:
       Occupied  (A') (A')
 (A') (A') (A") (A') (A') (A') (A') (A')
                 (A") (A')
 (A') (A') (A') (A') (A") (A') (A') (A")
                 (A') (A')
 (A") (A')
       Virtual   (A") (A') (A") (A') (A') (A")
 (A') (A') (A') (A')
                 (A") (A') (A') (A") (A') (A')
 (A') (A") (A') (A')
                 (A') (A") (A') (A') (A')
 (A") (A') (A") (A') (A')
                 (A') (A')
 ExpMin=
 4.11D-02 ExpMax= 6.11D+04 ExpMxC= 9.18D+03 IAcc=3 IRadAn=         5 AccDes=
 0.00D+00
 Harris functional with IExCor=  402 and IRadAn=       5
 diagonalized for initial guess.
 HarFok:  IExCor=  402 AccDes= 0.00D+00
 IRadAn=         5 IDoV= 1 UseB2=F ITyADJ=14
 ICtDFT=  3500011 ScaDFX=
 1.000000  1.000000  1.000000  1.000000
 FoFCou: FMM=F IPFlag=           0
 FMFlag=      100000 FMFlg1=           0
         NFxFlg=           0 DoJE=T
 BraDBF=F KetDBF=T FulRan=T
         wScrn=  0.000000 ICntrl=       500 IOpCl=
 0 I1Cent=   200000004 NGrid=           0
         NMat0=    1 NMatS0=      1
 NMatT0=    0 NMatD0=    1 NMtDS0=    0 NMtDT0=    0
 Petite list used in
 FoFCou.
 Keep R1 ints in memory in symmetry-blocked form, NReq=2159799.

 Requested convergence on RMS density matrix=1.00D-08 within 128 cycles.

 Requested convergence on MAX density matrix=1.00D-06.
 Requested convergence
 on             energy=1.00D-06.
 No special actions if energy rises.
 SCF
 Done:  E(RB3LYP) =  -1451.86533909     A.U. after   18 cycles

 NFock= 18  Conv=0.23D-08     -V/T= 2.0018
 Calling FoFJK, ICntrl=      2127
 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0.
 ***** Axes
 restored to original set *****
 Center     Atomic                   Forces
 (Hartrees/Bohr)
 Number     Number              X              Y
 Z
      1       26          -0.021775369    0.002114287    0.000000000

 2        8           0.036955110    0.014737157    0.000000000
      3
 6          -0.039695691   -0.040384091    0.000000000
      4        8
 0.024515951    0.023532647   -0.000000000
 Cartesian Forces:  Max
 0.040384091 RMS     0.023135364


 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad

 Berny optimization.
 Using GEDIIS/GDIIS optimizer.
 FormGI is forming the
 generalized inverse of G from B-inverse, IUseBI=4.
 Internal  Forces:  Max
 0.033908365 RMS     0.018980685
 Search for a local minimum.
 Step number
 2 out of a maximum of   20
 All quantities printed in internal units
 (Hartrees-Bohrs-Radians)
 Mixed Optimization -- RFO/linear search
 Update
 second derivatives using D2CorX and points    1    2
 DE= -1.54D-02
 DEPred=-1.23D-02 R= 1.26D+00
 TightC=F SS=  1.41D+00  RLast= 2.52D-01 DXNew=
 5.0454D-01 7.5596D-01
 Trust test= 1.26D+00 RLast= 2.52D-01 DXMaxT set to
 5.05D-01
 The second derivative matrix:
                          R1
 R2        R3        A1        A2
           R1           0.18668

 R2           0.04604   0.76870
           R3          -0.08608   0.12904
 1.50110
           A1           0.00316   0.00128   0.01538   0.25104

 A2          -0.00501   0.00702  -0.00784   0.00077   0.05407
           A3
 0.00000  -0.00000   0.00000   0.00000   0.00000

 A3
           A3           0.05456
 ITU=  1  0
 Use linear search
 instead of GDIIS.
     Eigenvalues ---    0.05364   0.05456   0.17607
 0.25109   0.75296
     Eigenvalues ---    1.52783
 RFO step:
 Lambda=-2.40357398D-03 EMin= 5.36398691D-02
 Quartic linear search produced a
 step of  0.74433.
 Iteration  1 RMS(Cart)=  0.12055350 RMS(Int)=
 0.00970928
 Iteration  2 RMS(Cart)=  0.01171440 RMS(Int)=  0.00007671

 Iteration  3 RMS(Cart)=  0.00008339 RMS(Int)=  0.00000000
 Iteration  4
 RMS(Cart)=  0.00000000 RMS(Int)=  0.00000000
 ClnCor:  largest displacement
 from symmetrization is 4.24D-12 for atom     3.
 Variable       Old X
 -DE/DX   Delta X   Delta X   Delta X     New X

 (Linear)    (Quad)   (Total)
    R1        3.63490   0.02187   0.14559
 0.04745   0.19304   3.82794
    R2        2.34327  -0.02250  -0.02587
 -0.02538  -0.05125   2.29202
    R3        2.18993   0.03391   0.06113
 -0.01980   0.04133   2.23126
    A1        2.10408  -0.00172   0.00721
 -0.01780  -0.01059   2.09349
    A2        3.27271   0.00495   0.09759
 0.11009   0.20769   3.48040
    A3        3.14159   0.00000   0.00000
 0.00000   0.00000   3.14159
         Item               Value     Threshold
 Converged?
 Maximum Force            0.033908     0.000450     NO 
 RMS
 Force            0.018981     0.000300     NO 
 Maximum Displacement
 0.157853     0.001800     NO 
 RMS     Displacement     0.126480     0.001200
 NO 
 Predicted change in Energy=-2.644271D-03

 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad


 Input orientation:                          
 Center     Atomic      Atomic
 Coordinates (Angstroms)
 Number     Number       Type             X
 Y           Z
      1         26           0        2.586226    8.170844
 5.000000
      2          8           0        4.611490    8.130764
 5.000000
      3          6           0        5.237660    9.169515
 5.000000
      4          8           0        6.148665    9.920644
 5.000000
                    Distance matrix (angstroms):

 1          2          3          4
     1  Fe   0.000000
     2  O
 2.025661   0.000000
     3  C    2.833275   1.212885   0.000000
     4  O
 3.968976   2.359359   1.180730   0.000000
 Stoichiometry    CFeO2

 Framework group  CS[SG(CFeO2)]
 Deg. of freedom     5
 Full point group
 CS      NOp   2
 Largest Abelian subgroup         CS      NOp   2
 Largest
 concise Abelian subgroup C1      NOp   1
                         Standard
 orientation:                         
 Center     Atomic      Atomic
 Coordinates (Angstroms)
 Number     Number       Type             X
 Y           Z
      1         26           0       -0.994550   -0.879340
 -0.000000
      2          8           0       -0.000000    0.885361
 0.000000
      3          6           0        1.212831    0.896868
 0.000000
      4          8           0        2.322666    1.299844
 0.000000
 Rotational constants (GHZ):          47.4271405           2.0987230
 2.0097869
 Standard basis: 6-31G (6D, 7F)
 There are    42 symmetry
 adapted cartesian basis functions of A'  symmetry.
 There are    14 symmetry
 adapted cartesian basis functions of A"  symmetry.
 There are    42
 symmetry adapted basis functions of A'  symmetry.
 There are    14 symmetry
 adapted basis functions of A"  symmetry.
    56 basis functions,   160
 primitive gaussians,    56 cartesian basis functions
    24 alpha electrons
 24 beta electrons
       nuclear repulsion energy       168.0152669884
 Hartrees.
 NAtoms=    4 NActive=    4 NUniq=    4 SFac= 1.00D+00 NAtFMM=   60
 NAOKFM=F Big=F
 Integral buffers will be    131072 words long.
 Raffenetti
 2 integral format.
 Two-electron integral symmetry is turned on.

 One-electron integrals computed using PRISM.
 NBasis=    56 RedAO= T EigKep=
 1.76D-03  NBF=    42    14
 NBsUse=    56 1.00D-06 EigRej= -1.00D+00 NBFU=
 42    14
 Initial guess from the checkpoint file:
 "step_000_DFT.chk"
 B after Tr=     0.000000   -0.000000
 -0.000000
         Rot=    0.998838   -0.000000   -0.000000   -0.048193 Ang=
 -5.52 deg.
 Initial guess orbital symmetries:
       Occupied  (A') (A')
 (A') (A') (A") (A') (A') (A') (A') (A')
                 (A") (A')
 (A') (A') (A') (A') (A") (A') (A') (A")
                 (A') (A')
 (A") (A')
       Virtual   (A') (A") (A') (A") (A') (A")
 (A') (A') (A') (A')
                 (A") (A') (A') (A") (A') (A')
 (A') (A") (A') (A')
                 (A') (A") (A') (A') (A')
 (A") (A') (A") (A') (A')
                 (A') (A')
 ExpMin=
 4.11D-02 ExpMax= 6.11D+04 ExpMxC= 9.18D+03 IAcc=3 IRadAn=         5 AccDes=
 0.00D+00
 Harris functional with IExCor=  402 and IRadAn=       5
 diagonalized for initial guess.
 HarFok:  IExCor=  402 AccDes= 0.00D+00
 IRadAn=         5 IDoV= 1 UseB2=F ITyADJ=14
 ICtDFT=  3500011 ScaDFX=
 1.000000  1.000000  1.000000  1.000000
 FoFCou: FMM=F IPFlag=           0
 FMFlag=      100000 FMFlg1=           0
         NFxFlg=           0 DoJE=T
 BraDBF=F KetDBF=T FulRan=T
         wScrn=  0.000000 ICntrl=       500 IOpCl=
 0 I1Cent=   200000004 NGrid=           0
         NMat0=    1 NMatS0=      1
 NMatT0=    0 NMatD0=    1 NMtDS0=    0 NMtDT0=    0
 Petite list used in
 FoFCou.
 Keep R1 ints in memory in symmetry-blocked form, NReq=2159799.

 Requested convergence on RMS density matrix=1.00D-08 within 128 cycles.

 Requested convergence on MAX density matrix=1.00D-06.
 Requested convergence
 on             energy=1.00D-06.
 No special actions if energy rises.
 SCF
 Done:  E(RB3LYP) =  -1451.86779894     A.U. after   19 cycles

 NFock= 19  Conv=0.32D-08     -V/T= 2.0018
 Calling FoFJK, ICntrl=      2127
 FMM=F ISym2X=1 I1Cent= 0 IOpClX= 0 NMat=1 NMatS=1 NMatT=0.
 ***** Axes
 restored to original set *****
 Center     Atomic                   Forces
 (Hartrees/Bohr)
 Number     Number              X              Y
 Z
      1       26          -0.002475531    0.002170910    0.000000000

 2        8          -0.009275511   -0.015400826    0.000000000
      3
 6           0.012873515    0.005174131    0.000000000
      4        8
 -0.001122473    0.008055785   -0.000000000
 Cartesian Forces:  Max
 0.015400826 RMS     0.007028017


 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad

 Berny optimization.
 Using GEDIIS/GDIIS optimizer.
 FormGI is forming the
 generalized inverse of G from B-inverse, IUseBI=4.
 Internal  Forces:  Max
 0.017401591 RMS     0.010265616
 Search for a local minimum.
 Step number
 3 out of a maximum of   20
 All quantities printed in internal units
 (Hartrees-Bohrs-Radians)
 Mixed Optimization -- RFO/linear search
 Update
 second derivatives using D2CorX and points    1    2    3
 DE= -2.46D-03
 DEPred=-2.64D-03 R= 9.30D-01
 TightC=F SS=  1.41D+00  RLast= 2.91D-01 DXNew=
 8.4853D-01 8.7386D-01
 Trust test= 9.30D-01 RLast= 2.91D-01 DXMaxT set to
 8.49D-01
 The second derivative matrix:
                          R1
 R2        R3        A1        A2
           R1           0.14042

 R2           0.04009   0.84593
           R3          -0.15330   0.08559
 1.42002
           A1           0.01583  -0.02335   0.04566   0.25643

 A2           0.00387  -0.03883   0.02611   0.01417   0.08070
           A3
 0.00000  -0.00000   0.00000   0.00000   0.00000

 A3
           A3           0.05456
 ITU=  1  1  0
 Use linear search
 instead of GDIIS.
     Eigenvalues ---    0.05456   0.07570   0.11658
 0.25847   0.84223
     Eigenvalues ---    1.45052
 RFO step:
 Lambda=-2.28883397D-03 EMin= 5.45649275D-02
 Quartic linear search produced a
 step of -0.27572.
 Iteration  1 RMS(Cart)=  0.11082651 RMS(Int)=
 0.00968836
 Iteration  2 RMS(Cart)=  0.01008655 RMS(Int)=  0.00002336

 Iteration  3 RMS(Cart)=  0.00002996 RMS(Int)=  0.00000000
 Iteration  4
 RMS(Cart)=  0.00000000 RMS(Int)=  0.00000000
 ClnCor:  largest displacement
 from symmetrization is 3.37D-09 for atom     3.
 Variable       Old X
 -DE/DX   Delta X   Delta X   Delta X     New X

 (Linear)    (Quad)   (Total)
    R1        3.82794   0.00252  -0.05323
 0.09099   0.03776   3.86570
    R2        2.29202   0.01740   0.01413
 -0.00542   0.00871   2.30074
    R3        2.23126   0.00426  -0.01140
 0.02206   0.01067   2.24192
    A1        2.09349  -0.00809   0.00292
 -0.02802  -0.02510   2.06839
    A2        3.48040  -0.01548  -0.05726
 -0.11944  -0.17670   3.30370
    A3        3.14159   0.00000   0.00000
 0.00000   0.00000   3.14159
         Item               Value     Threshold
 Converged?
 Maximum Force            0.017402     0.000450     NO 
 RMS
 Force            0.010266     0.000300     NO 
 Maximum Displacement
 0.128723     0.001800     NO 
 RMS     Displacement     0.114165     0.001200
 NO 
 Predicted change in Energy=-1.691720D-03

 GradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad


 Input orientation:                          
 Center     Atomic      Atomic
 Coordinates (Angstroms)
 Number     Number       Type             X
 Y           Z
      1         26           0        2.587635    8.230504
 5.000000
      2          8           0        4.627577    8.077882
 5.000000
      3          6           0        5.286906    9.101397
 5.000000
      4          8           0        6.081924    9.981983
 5.000000
                    Distance matrix (angstroms):

 1          2          3          4
     1  Fe   0.000000
     2  O
 2.045643   0.000000
     3  C    2.836286   1.217497   0.000000
     4  O
 3.908674   2.395981   1.186375   0.000000
 Stoichiometry    CFeO2

 Framework group  CS[SG(CFeO2)]
 Deg. of freedom     5
 Full point group
 CS      NOp   2
 Largest Abelian subgroup         CS      NOp   2
 Largest
 concise Abelian subgroup C1      NOp   1
                         Standard
 orientation:                         
 Center     Atomic      Atomic
 Coordinates (Angstroms)
 Number     Number       Type             X
 Y           Z