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Re: XANES for benzene



Dear M. Koshino,

I attacehed the feff.inp file and the output of the feff8.2 for that file.
I modified your input file and changed many cards. I also like the ATOMS program to make feff.inp files, but typically I do not use the defaults and modify cards a lot. Here are the changes I made

EXCHANGE  2  1  0
  ixc=2 uses no self-energy shifts, and seems to give best agreement
   in your case; often the default ixc=0 is the best; for f-elements
   often ixc=3 is the best
  vr = 1 to see 1 eV below the Fermi level; feff8.2 sometimews puts
  Fermi level too high. I never used vr>2.

AFOLP  1.4
  this card often produces better potentials for open structures
like hydrocarbon molecules or for tetrahedral coordination.
(default is AFOLP 1.15 seems to better for solid state applications)

DEBYE  100  400
  I tried to simulate temperature effects; but in this case of soft
hydrogen bonds between molecules and strong covalent bonds within the
molecules the Correlated Debye model does not seem to work well. The
model assumes that all bonds are of similar strength.

SCF 3.5
  You had TOO BIG radius here. Typically I use the Rscf=3.5-4.2 Angstroms
to have about 15-25 atoms in clusters. This is used to calculate the
smooth quantity- charge density and potential. Do not need to use
huge clusters here. Chemical bonds are local, and charge around the atom
should not depend on very distant atoms.

FMS  3.5
  This chooses a cluster of 16 atoms with only 6 carbon atoms included.
Effectively it one benzene circle. This seems to be enough here.
To get close to the band structure results we typically need more
that 150 atoms in cluster. The same holds for XANES calculations,
for Si we used as much as 850 atom clusters. (Ankudinov et al.,
PRB 65, 104107 (2002)).

 POTENTIALS
 *    ipot   Z  element            l_scmt  l2fms   stoichiometry
        0    6   C                  2       3       0.1
        1    6   C                  2       3       3.9
        2    1   H                  2       3       4
 Here I always make changes to the ATOMS output. Usually I increase
l_scmt cards ( use -1: the feff8.2 defaults usually better choice)
l_fms I typically make 3, since it in principle how high in energy
you can trust feff8.2
stoichiometry: ATOMS usually puts too small value for the absorber
(0.001) which often causes problems for the self-consistency loop.
The higher relative weight 1-5 % helps self-consistency enormously.

 This result I get with these cards (xmu.dat is attached) is closest
I could get to Fig.1 of the Horsley et al paper. The peak A of feff8.2
is too broad. This is typical for pi* resonance and we discussed the
reason for that ealier. (See e.g. paper
on"Shape resonances of oriented molecules: ab initio theory and
experiment on hydrocarbon molecules" , Haack et al., PRL 84 (2000) 614.)
Also the peak C seems to be too big. However the peak positions
look in reasonable agreement to experimental data:
Thus in experiment peak to peak distances are ( AB-3.9; AC 8.5; AD 15 eV),
while in calculation are (4.3 10.2 and 15.5). Since errobar is about 0.5
agreement is not bad.

Let me know if you think agreement is still not satisfactory.
I also used calculation for larger cluster of 102 atoms, to simulate
solid state data; but  the agreement gets worse than the calculations
for 16 atoms. Probably bonds between benzene molecules are much softer than the bonds between atoms of one molecule. Then Debye-Waller factors
then can wash out the the structure due to distant atoms.

Also I did sometimes calculation for Glycine ( unpublished). There two
carbon atoms are not equivalent and to get agreement with experiment
you cannot use the same potential type for 2 carbon atoms. You can use
the same potential type only for carbons that have the same nearest
neighbors.

Best wishes
Dr. Alexei Ankudinov

TITLE BENZENE

 *  C K edge energy = 284.20 eV
 EDGE      K
 S02       1.0

 *         pot    xsph  fms   paths genfmt ff2chi
*CONTROL   1      1     1     1     1      1
 CONTROL   0      1     1     1     1      1
*PRINT     1      0     0     0     0      0
 EXCHANGE  2  1  0
 AFOLP 1.4
 DEBYE  100  400

                          *** ixc=0 means to use Hedin-Lundqvist
 *         rfms1 [lfms1 nscmt ca nmix]
 SCF       3.5
 *         [xkmax xkstep estep]
 XANES     4. .05 .3

 *         r_fms     l_fms
 FMS        3.5  0
*FMS        6.2  0

 RPATH     0.1

 POTENTIALS
 *    ipot   Z  element            l_scmt  l2fms   stoichiometry
        0    6   C                  2       3       0.1
        1    6   C                  2       3       3.9
        2    1   H                  2       3       4

 ATOMS                          * this list contains 136 atoms
 *   x          y          z      ipot  tag           distance
    0.00000    0.00000    0.00000  0    C1            0.00000     0
    0.30362   -1.02460   -0.08652  2    H1            1.07214     1
   -1.00188    0.44657   -0.87292  1    C3            1.40185     2
    0.57144    0.89604    0.92708  1    C2            1.41029     3
   -1.44724   -0.23585   -1.58828  2    H3            2.16166     4
    1.37264    0.57319    1.59812  2    H2            2.18327     5
    0.15293    2.23478    0.94889  1    C3            2.43270     6
   -1.42038    1.78531   -0.85111  1    C2            2.43499     7
   -0.84895    2.68135    0.07597  1    C1            2.81356     8
    2.28276   -0.23585   -1.85276  2    H3            2.94946     9
   -1.44724   -1.91580    1.92872  2    H3            3.07973    10
   -2.35736    0.57319    1.99484  2    H2            3.14087    11
    1.50841    2.10815   -1.91888  2    H2            3.22517    12
    0.59829    2.91720    1.66424  2    H3            3.41141    13
    2.28276   -1.91580    1.66424  2    H3            3.41335    14
   -2.22159    2.10815   -1.52216  2    H2            3.42005    15
    1.37264   -2.72485   -1.91888  2    H2            3.60431    16
   -3.42638   -1.12706    0.16249  2    H1            3.61064    17
    0.30362   -1.12706    3.43048  2    H1            3.62362    18
    2.72812    0.44657   -2.56811  1    C3            3.77323    19
    0.30362   -1.12706   -3.60352  2    H1            3.78785    20
   -1.00188   -2.59822    2.64408  1    C3            3.84001    21
   -1.15257    3.70594    0.16249  2    H1            3.88443    22
    2.72812   -2.59822    0.94889  1    C3            3.88507    23
    2.30962    1.78531   -2.58992  1    C2            3.90248    24
   -2.35736   -2.72485   -1.52216  2    H2            3.91138    25
    0.57144   -3.04769   -2.58992  1    C2            4.04013    26
    0.00000   -2.15165    3.51700  1    C1            4.12297    27
    0.00000   -2.15165   -3.51700  1    C1            4.12297    28
    4.03362   -1.12706    0.16249  2    H1            4.19127    29
   -3.15856    0.89604    2.66589  1    C2            4.22923    30
    3.73000   -2.15165    0.07597  1    C1            4.30677    31
   -3.73000   -2.15165    0.07597  1    C1            4.30677    32
   -3.15856   -3.04769   -0.85111  1    C2            4.47094    33
    2.57743    3.80840   -0.08652  2    H1            4.59941    34
    2.30962   -3.93696    0.92708  1    C2            4.65763    35
   -3.13171    2.91720    1.92872  2    H3            4.69442    36
    1.50841   -4.25981    1.59812  2    H2            4.79325    37
   -3.42638   -1.02460   -3.35451  2    H1            4.90333    38
   -1.42038   -3.93696    2.66589  1    C2            4.96227    39
   -3.57707    2.23478    2.64408  1    C3            4.97803    40
    0.59829    4.59715   -1.85276  2    H3            4.99244    41
    3.73000    0.00000   -3.44103  1    C1            5.07480    42
   -3.73000    0.00000   -3.44103  1    C1            5.07480    43
    0.15293   -4.38643   -2.56811  1    C3            5.08521    44
   -3.42638   -1.02460    3.67949  2    H1            5.13113    45
    4.30144    0.89604    2.66589  1    C2            5.13928    46
    3.73000    0.00000    3.59297  1    C1            5.17903    47
   -3.73000    0.00000    3.59297  1    C1            5.17903    48
   -1.00188   -2.59822   -4.38992  1    C3            5.19864    49
   -2.22159   -4.25981    1.99484  2    H2            5.20200    50
    3.88293    2.23478    2.64408  1    C3            5.20217    51
   -1.15257    3.80840   -3.35451  2    H1            5.20433    52
    2.72812    0.44657    4.46589  1    C3            5.25226    53
    2.88105    2.68135    3.51700  1    C1            5.27820    54
    2.88105    2.68135   -3.51700  1    C1            5.27820    55
    2.30962    1.78531    4.44408  1    C2            5.31710    56
    4.30144   -3.04769   -0.85111  1    C2            5.33996    57
    4.03362   -1.02460   -3.35451  2    H1            5.34534    58
   -4.73188    0.44657   -2.56811  1    C3            5.40234    59
    0.57144   -3.04769    4.44408  1    C2            5.41893    60
   -1.15257    3.80840    3.67949  2    H1            5.41950    61
    0.59829   -5.06885   -1.85276  2    H3            5.42991    62
   -3.15856    0.89604   -4.36811  1    C2            5.46441    63
   -4.73188   -2.59822    0.94889  1    C3            5.48104    64
   -5.17724   -0.23585   -1.85276  2    H3            5.50383    65
    5.10264    0.57319    1.99484  2    H2            5.50862    66
    4.03362   -1.02460    3.67949  2    H1            5.55505    67
    4.32829    2.91720    1.92872  2    H3            5.56454    68
   -2.35736    0.57319   -5.03916  2    H2            5.59275    69
    2.88105    4.83300    0.00000  1    C1            5.62657    70
    2.88105   -4.83300    0.00000  1    C1            5.62657    71
    1.37264    0.57319   -5.43588  2    H2            5.63573    72
   -1.44724   -0.23585    5.44572  2    H3            5.63968    73
   -1.44724   -1.91580   -5.10528  2    H3            5.64169    74
    2.28276   -0.23585    5.18124  2    H3            5.66673    75
    2.57743    3.70594    3.43048  2    H1            5.66969    76
   -3.57707   -4.38643   -0.87292  1    C3            5.72697    77
    1.50841    2.10815    5.11512  2    H2            5.73446    78
   -5.17724   -1.91580    1.66424  2    H3            5.76574    79
    2.57743    3.70594   -3.60352  2    H1            5.77603    80
   -3.13171    4.59715   -1.58828  2    H3            5.78481    81
    1.50841    5.40619    1.59812  2    H2            5.83577    82
    5.23841    2.10815   -1.52216  2    H2            5.84827    83
    0.15293    5.27957   -2.56811  1    C3            5.87303    84
    3.88293   -4.38643   -0.87292  1    C3            5.92283    85
    1.37264   -2.72485    5.11512  2    H2            5.95596    86
    5.10264   -2.72485   -1.52216  2    H2            5.98153    87
   -0.84895    4.83300   -3.44103  1    C1            5.99327    88
   -0.84895   -4.83300   -3.44103  1    C1            5.99327    89
   -5.15038    1.78531   -2.58992  1    C2            6.03502    90
   -1.42038   -3.93696   -4.36811  1    C2            6.04959    91
   -1.15257   -5.96006    0.16249  2    H1            6.07265    92
   -0.84895    4.83300    3.59297  1    C1            6.08178    93
   -0.84895   -4.83300    3.59297  1    C1            6.08178    94
   -3.57707    2.23478   -4.38992  1    C3            6.08778    95
    0.59829    2.91720   -5.36976  2    H3            6.14022    96
    2.28276   -1.91580   -5.36976  2    H3            6.14130    97
   -3.13171   -5.06885   -1.58828  2    H3            6.16632    98
   -2.22159    5.40619    1.99484  2    H2            6.17590    99
   -4.88257    3.80840   -0.08652  2    H1            6.19281   100
    4.30144    0.89604   -4.36811  1    C2            6.19562   101
    0.57144    0.89604   -6.10692  1    C2            6.19870   102
END
# BENZENE                                                        Feff 8.20   
# POT  SCF  30  3.5000   0, core-hole, AFOLP (folp(0)= 1.400)
# Abs   Z= 6 Rmt= 0.927 Rnm= 1.022 K  shell
# Pot 1 Z= 6 Rmt= 0.947 Rnm= 1.046
# Pot 2 Z= 1 Rmt= 0.819 Rnm= 0.894
# Gam_ch=8.676E-02 Gd state Vi= 0.000E+00 Vr= 1.000E+00
# Mu=-9.515E+00 kf=2.662E+00 Vint=-1.582E+01 Rs_int= 1.362
# FMS rfms= 3.5000
# PATH  Rmax= 0.100,  Keep_limit= 0.00, Heap_limit 0.00  Pwcrit= 2.50%
#  S02=1.000  Temp= 100.00  Debye_temp= 400.00  Global_sig2= 0.00000
#  Curved wave amplitude ratio filter   4.000%
#     file         sig2 tot  cw amp ratio   deg  nlegs   reff  inp sig2
#     0/   0 paths used
#  xsedge+ 50, used to normalize mu           7.1036E-03
#  -----------------------------------------------------------------------
#  omega    e    k    mu    mu0     chi     @#
     272.180    -15.125  -1.100  9.43792E-04  7.27191E-03 -6.32811E-03
     272.980    -14.325  -1.000  1.45615E-03  9.46132E-03 -8.00516E-03
     273.704    -13.601  -0.900  2.30825E-03  1.25946E-02 -1.02863E-02
     274.351    -12.954  -0.800  3.76520E-03  1.72359E-02 -1.34707E-02
     274.923    -12.382  -0.700  6.31706E-03  2.44113E-02 -1.80942E-02
     275.418    -11.887  -0.600  1.08529E-02  3.61245E-02 -2.52716E-02
     275.837    -11.468  -0.500  1.89109E-02  5.66786E-02 -3.77678E-02
     276.180    -11.125  -0.400  3.31276E-02  9.66043E-02 -6.34767E-02
     276.447    -10.858  -0.300  5.94801E-02  1.86971E-01 -1.27491E-01
     276.490    -10.815  -0.281  6.72557E-02  2.17026E-01 -1.49770E-01
     276.790    -10.515   0.000  5.96658E-01  2.77056E+00 -2.17390E+00
     277.090    -10.215   0.281  1.20633E+00  4.92526E+00 -3.71893E+00
     277.390     -9.915   0.397  1.38086E+00  4.61816E+00 -3.23730E+00
     277.690     -9.615   0.486  1.59059E+00  4.29252E+00 -2.70193E+00
     277.990     -9.315   0.561  1.85562E+00  4.00202E+00 -2.14640E+00
     278.290     -9.015   0.627  2.16948E+00  3.74887E+00 -1.57939E+00
     278.590     -8.715   0.687  2.48038E+00  3.52852E+00 -1.04814E+00
     278.890     -8.415   0.742  2.68205E+00  3.33601E+00 -6.53965E-01
     278.933     -8.372   0.750  2.69220E+00  3.31045E+00 -6.18257E-01
     279.228     -8.077   0.800  2.67002E+00  3.14696E+00 -4.76949E-01
     279.542     -7.763   0.850  2.47052E+00  2.99322E+00 -5.22700E-01
     279.876     -7.429   0.900  2.19843E+00  2.84973E+00 -6.51294E-01
     280.228     -7.077   0.950  1.95244E+00  2.71594E+00 -7.63504E-01
     280.600     -6.705   1.000  1.77382E+00  2.59187E+00 -8.18052E-01
     280.990     -6.315   1.050  1.66472E+00  2.47676E+00 -8.12036E-01
     281.400     -5.905   1.100  1.61630E+00  2.37042E+00 -7.54122E-01
     281.828     -5.477   1.150  1.62053E+00  2.27207E+00 -6.51539E-01
     282.276     -5.029   1.200  1.67152E+00  2.18120E+00 -5.09677E-01
     282.743     -4.562   1.250  1.75331E+00  2.09729E+00 -3.43982E-01
     283.229     -4.076   1.300  1.81315E+00  2.01967E+00 -2.06521E-01
     283.733     -3.572   1.350  1.78007E+00  1.94810E+00 -1.68030E-01
     284.257     -3.048   1.400  1.67975E+00  1.88189E+00 -2.02135E-01
     284.800     -2.505   1.450  1.60867E+00  1.82077E+00 -2.12106E-01
     285.362     -1.943   1.500  1.61165E+00  1.76407E+00 -1.52420E-01
     285.943     -1.362   1.550  1.69657E+00  1.71165E+00 -1.50835E-02
     286.543     -0.762   1.600  1.87093E+00  1.66311E+00  2.07819E-01
     287.162     -0.143   1.650  2.14662E+00  1.61803E+00  5.28583E-01
     287.801      0.496   1.700  2.51781E+00  1.57628E+00  9.41531E-01
     288.458      1.153   1.750  2.91103E+00  1.53745E+00  1.37358E+00
     289.134      1.829   1.800  3.16335E+00  1.50139E+00  1.66196E+00
     289.829      2.524   1.850  3.14893E+00  1.46783E+00  1.68110E+00
     290.544      3.239   1.900  2.92694E+00  1.43650E+00  1.49044E+00
     291.277      3.972   1.950  2.64880E+00  1.40754E+00  1.24126E+00
     292.030      4.725   2.000  2.41416E+00  1.38035E+00  1.03381E+00
     292.801      5.496   2.050  2.25959E+00  1.35506E+00  9.04536E-01
     293.592      6.287   2.100  2.18845E+00  1.33145E+00  8.57001E-01
     294.401      7.096   2.150  2.17911E+00  1.30940E+00  8.69709E-01
     295.230      7.925   2.200  2.16623E+00  1.28878E+00  8.77449E-01
     296.078      8.773   2.250  2.06130E+00  1.26951E+00  7.91785E-01
     296.945      9.640   2.300  1.86422E+00  1.25146E+00  6.12762E-01
     297.830     10.525   2.350  1.65864E+00  1.23455E+00  4.24089E-01
     298.735     11.430   2.400  1.49433E+00  1.21870E+00  2.75634E-01
     299.659     12.354   2.450  1.37393E+00  1.20382E+00  1.70114E-01
     300.602     13.297   2.500  1.28571E+00  1.18984E+00  9.58777E-02
     301.564     14.259   2.550  1.21911E+00  1.17671E+00  4.24037E-02
     302.545     15.240   2.600  1.16725E+00  1.16432E+00  2.93490E-03
     303.545     16.240   2.650  1.12613E+00  1.15266E+00 -2.65250E-02
     304.564     17.259   2.700  1.09321E+00  1.14164E+00 -4.84283E-02
     305.603     18.298   2.750  1.06681E+00  1.13121E+00 -6.44057E-02
     306.660     19.355   2.800  1.04572E+00  1.12133E+00 -7.56092E-02
     307.736     20.431   2.850  1.02907E+00  1.11194E+00 -8.28710E-02
     308.832     21.527   2.900  1.01620E+00  1.10300E+00 -8.67967E-02
     309.946     22.641   2.950  1.00662E+00  1.09446E+00 -8.78358E-02
     311.080     23.775   3.000  9.99912E-01  1.08627E+00 -8.63598E-02
     312.232     24.927   3.050  9.95673E-01  1.07842E+00 -8.27469E-02
     313.404     26.099   3.100  9.93343E-01  1.07083E+00 -7.74918E-02
     314.594     27.289   3.150  9.92187E-01  1.06349E+00 -7.13006E-02
     315.804     28.499   3.200  9.91241E-01  1.05636E+00 -6.51234E-02
     317.033     29.728   3.250  9.89356E-01  1.04939E+00 -6.00378E-02
     318.280     30.975   3.300  9.85617E-01  1.04256E+00 -5.69467E-02
     319.547     32.242   3.350  9.79618E-01  1.03585E+00 -5.62274E-02
     320.833     33.528   3.400  9.71627E-01  1.02920E+00 -5.75699E-02
     322.138     34.833   3.450  9.62465E-01  1.02260E+00 -6.01383E-02
     323.462     36.157   3.500  9.53095E-01  1.01602E+00 -6.29289E-02
     324.805     37.500   3.550  9.44352E-01  1.00943E+00 -6.50766E-02
     326.167     38.862   3.600  9.36807E-01  1.00281E+00 -6.59988E-02
     327.548     40.243   3.650  9.30725E-01  9.96125E-01 -6.54000E-02
     328.948     41.643   3.700  9.26167E-01  9.89374E-01 -6.32075E-02
     330.368     43.063   3.750  9.23021E-01  9.82524E-01 -5.95034E-02
     331.806     44.501   3.800  9.21108E-01  9.75575E-01 -5.44672E-02
     333.263     45.958   3.850  9.20130E-01  9.68471E-01 -4.83409E-02
     334.740     47.435   3.900  9.19834E-01  9.61239E-01 -4.14051E-02
     336.235     48.930   3.950  9.19895E-01  9.53853E-01 -3.39572E-02
     337.749     50.444   4.000  9.20001E-01  9.46297E-01 -2.62958E-02