[CPMD-list] help on the kohn-sham energies!

=?gb2312?B?U2hhbmd5aSBNYQ==?= shyma at imr.ac.cn
Tue Dec 13 09:37:30 CET 2005


Dear axel and cpmd-users:  
    Thanks for your kindly reply!
    Today I have other questions need your help! 
    Firstly, I have optimized the wavefunction of the 5 atoms clusters and recalculated the kohn-sham energyes of it, but I find the final total energys is different,but I don't know what's the reason cause the difference. The following are the input and out files in different calculation respectively:

input file for the wavefunction optimization:
*********************************************
&CPMD
  OPTIMIZE WAVEFUNCTION
  CONVERGENCE ORBITALS
  1.0D-5
  FREE ENERGY FUNCTIONAL
  LANCZOS DIAGONALISATION
  LANCZOS PARAMETAERS N=5
  1  6  20  1.0D-9
  0.05  1.0D-10
  0.01  1.0D-12
  0.0025  1.0D-14
  0.001  1.0D-16
  ANDERSON MIXING
  0.2
  BROYDEN MIXING
  BROYMIX=0.15
  TEMPERATURE ELCECTRON
  1000
  CENTER MOLECULE ON
  MAXSTEP
  1000
  STRUCTURE BONDS ANGLES
  MIRROR
&END

&SYSTEM
  SYMMETRY
  0
  POISSON SOLVER TUCKERMAN
  ANGSTROM
  CELL
  18.0  1.0  1.0  0.0  0.0  0.0
  STATES
  12
  CUTOFF
  60
&END

&ATOMS
*Al_SGS_LDA.psp KLEINMAN-BYLANDER
 LMAX=D
 5
 9.627618698838     10.483425410635      8.869432662311
 10.799305233317    8.197179013185       8.528215175287 
 8.342182486388     8.284268303325       7.708984912400
 9.030290923963     8.232406355001       10.421762121950
 7.200662913258     9.802781813240       9.471731059454
&END

&DFT
  FUNCTIONAL LDA
&END

input for the khon-sham energies:
********************************
&CPMD
  KOHN-SHAM ENERGIES
  8
  RESTART WAVEFUNCTION COORDINATES
  FREE ENERGY FUNCTIONAL
  LANCZOS DIAGONALIZATION
  RHOOUT
  ELECTROSTATIC POTENTIAL
  ELF
  CONVERGENCE ORBITALS
  1.0D-5
  CENTER MOLECULE ON
  TEMPERATURE ELECTRON
  1000
  MIRROR
&END
                                                                          
&SYSTEM
  SYMMETRY
  0
  POISSON SOLVER TUCKERMAN
  ANGSTROM
  CELL
  18.0  1.0  1.0  0.0  0.0  0.0
  CUTOFF
  60
&END
                                                                          
&DFT
  FUNCTIONAL LDA
&END
                                                                          
&ATOMS
*Al_SGS_LDA.psp KLEINMAN-BYLANDER
 LMAX=D
 5
 9.627618698838     10.483425410635      8.869432662311
 10.799305233317    8.197179013185       8.528215175287
 8.342182486388     8.284268303325       7.708984912400
 9.030290923963     8.232406355001       10.421762121950
 7.200662913258     9.802781813240       9.471731059454
&END

the final results for the wavefunction optimization:
 ****************************************************************


 EIGENVALUES(EV) AND OCCUPATION:
     1    -12.1696122     2.000        2     -8.8559503     2.000
     3     -7.9476996     2.000        4     -7.9473935     2.000
     5     -5.7240799     2.000        6     -4.7316987     1.988
     7     -4.3800213     1.465        8     -4.3798610     1.464
     9     -3.9610614     0.041       10     -3.9609183NC   0.041
    11     -3.4441107NC   0.000       12     -1.4512370NC   0.000
 CHEMICAL POTENTIAL =                            -4.2932170551 EV

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


 ELECTRONIC GRADIENT:
    MAX. COMPONENT =    9.04632E-06         NORM =    2.01259E-06

 TOTAL INTEGRATED ELECTRONIC DENSITY
    IN G-SPACE =                                        15.000000
    IN R-SPACE =                                        15.000000

 (F+E2+X-V+O)           TOTAL ENERGY =          -10.13365518 A.U.
 (F)          ELECTRONIC FREE ENERGY =           -3.97233193 A.U.
 (E2=I-H-S+R)   ELECTROSTATIC ENERGY =           -7.20586331 A.U.
 (S)                           ESELF =           14.96033552 A.U.
 (R)                             ESR =            0.00054749 A.U.
 (X)     EXCHANGE-CORRELATION ENERGY =           -3.45753883 A.U.
 (V)     EXCHANGE-CORRELATION POTEN. =           -4.50207656 A.U.
 (O)    BOGOLIUBOV CORRECTION ENERGY =            0.00000233 A.U.
*****************************************************************

and final results for the kohn-sham energies:
 ****************************************************************
                                                                          
                                                                          
 EIGENVALUES(EV) AND OCCUPATION:
     1    -12.1738143     2.000        2     -8.8233432     2.000
     3     -8.2125551     2.000        4     -7.7129732     2.000
     5     -5.6818952     2.000        6     -4.8253746     1.999
     7     -4.5739314     1.979        8     -4.1403639     0.761
     9     -3.9798900     0.174       10     -3.9165498     0.087
    11     -3.3955067     0.000       12     -1.5688794     0.000
    13     -1.3219857     0.000       14     -0.8650114NC   0.000
    15     -0.7020890NC   0.000       16     -0.3384448NC   0.000
 CHEMICAL POTENTIAL =                            -4.1824507416 EV
                                                                          
 ****************************************************************
                                                                          
                                                                          
 ELECTRONIC GRADIENT:
    MAX. COMPONENT =    9.86609E-03         NORM =    2.54834E+00
                                                                          
 TOTAL INTEGRATED ELECTRONIC DENSITY
    IN G-SPACE =                                        15.000000
    IN R-SPACE =                                        15.000000
                                                                          
 (F+E2+X-V+O)           TOTAL ENERGY =          -10.15535475 A.U.
 (F)          ELECTRONIC FREE ENERGY =           -3.97978925 A.U.
 (E2=I-H-S+R)   ELECTROSTATIC ENERGY =           -7.22134101 A.U.
 (S)                           ESELF =           14.96033552 A.U.
 (R)                             ESR =            0.00054749 A.U.
 (X)     EXCHANGE-CORRELATION ENERGY =           -3.46149018 A.U.
 (V)     EXCHANGE-CORRELATION POTEN. =           -4.50726336 A.U.
 (O)    BOGOLIUBOV CORRECTION ENERGY =            0.00000233 A.U.
                                                                          
 ****************************************************************

You can see the difference what I mean from the above files. The final results "TOTAL ENERGY"  "EIGENVALUES(EV) AND OCCUPATION" and "CHEMICAL POTENTIAL(is it the Fermi energy?)" are all not the same for the wavefunction calculation and kohn-sham energies calculation. So what cause the difference and which results are more correct? Are there some faults in my 2 input files? 
  Secondly, what's the meaning of "NC" in the "EIGENVALUES(EV) AND OCCUPATION" results if the results show the occupation stats? Does it mean "not converged"? Is there any difference between the "13     -1.3219857     0.000 " and   "14     -0.8650114NC   0.000"? The occupation of all them are 0 and  "14" indentfied NC and "13" is not.

  Any comments and advices are appreciated!
  Thanks in advance!
  Best regards!
  shyma
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