[QE-users] Strange frequencies hard to interpret

Jibiao Li jibiaoli at foxmail.com
Sun Oct 6 13:35:36 CEST 2019


Dear QE experts,


I am studying mixed H2O/OH phase on close packed metal surfaces using QE 6.4.1. To my suprise, however, the calculated vibrational frequencies for the adsorbates are substantially different for the mixed H2O/OH phase on Ag(111) and Au(111) 


For the latter (on Au(111)), I obtained
 

     freq ( 46 - 46) =         48.0  [cm-1]   --> A               I+R
 

     freq ( 47 - 47) =        120.8  [cm-1]   --> A               I+R
 

     freq ( 48 - 48) =        145.1  [cm-1]   --> A               I+R
 

     freq ( 49 - 49) =        197.5  [cm-1]   --> A               I+R
 

     freq ( 50 - 50) =        280.7  [cm-1]   --> A               I+R
 

     freq ( 51 - 51) =        369.2  [cm-1]   --> A               I+R
 

     freq ( 52 - 52) =        575.0  [cm-1]   --> A               I+R
 

     freq ( 53 - 53) =        869.7  [cm-1]   --> A               I+R
 

     freq ( 54 - 54) =        873.8  [cm-1]   --> A               I+R
 

     freq ( 55 - 55) =        926.4  [cm-1]   --> A               I+R
 

     freq ( 56 - 56) =       1011.7  [cm-1]   --> A               I+R
 

     freq ( 57 - 57) =       1537.5  [cm-1]   --> A               I+R
 

     freq ( 58 - 58) =       3025.7  [cm-1]   --> A               I+R
 

     freq ( 59 - 59) =       3055.8  [cm-1]   --> A               I+R
 

     freq ( 60 - 60) =       3566.1  [cm-1]   --> A               I+R




Obviously, one OH stretching frequency of the adsorbed water is missing. Does anybody know why is this ?



 For the former (on Ag(111)), I got 
 
     freq ( 46 - 46) =         47.8  [cm-1]   --> A               I+R
 
     freq ( 47 - 47) =         49.8  [cm-1]   --> A               I+R
 
     freq ( 48 - 48) =         54.3  [cm-1]   --> A               I+R
 
     freq ( 49 - 49) =         80.1  [cm-1]   --> A               I+R
 
     freq ( 50 - 50) =         84.7  [cm-1]   --> A               I+R
 
     freq ( 51 - 51) =         99.0  [cm-1]   --> A               I+R
 
     freq ( 52 - 52) =        111.2  [cm-1]   --> A               I+R
 
     freq ( 53 - 53) =        117.9  [cm-1]   --> A               I+R
 
     freq ( 54 - 54) =        187.9  [cm-1]   --> A               I+R
 
     freq ( 55 - 55) =        849.4  [cm-1]   --> A               I+R
 
     freq ( 56 - 56) =       1005.9  [cm-1]   --> A               I+R
 
     freq ( 57 - 57) =       1572.9  [cm-1]   --> A               I+R
 
     freq ( 58 - 58) =       2824.8  [cm-1]   --> A               I+R
 
     freq ( 59 - 59) =       3670.5  [cm-1]   --> A               I+R
 
     freq ( 60 - 60) =       3782.1  [cm-1]   --> A               I+R




Why the two surfaces differ so much regarding the adsrobate frequencies ?




Ag111.SCF input


 &CONTROL
                 calculation = 'scf' ,
                restart_mode = 'from_scratch' ,
                      outdir = './' ,
                  pseudo_dir = '/home/jibiaoli/pseudo/' ,
                      prefix = 'sym' ,
                     tstress = .true. ,
                     tprnfor = .true. ,
 /
 &SYSTEM
                       ibrav = 0,
                   celldm(1) = 9.456004324,
                         nat = 20,
                        ntyp = 3,
                     ecutwfc = 49 ,
                     ecutrho = 411 ,
                 occupations = 'smearing' ,
                     degauss = 0.02 ,
                    smearing = 'methfessel-paxton' ,
                    vdw_corr = 'DFT-D',
 /
 &ELECTRONS
                 mixing_beta = 0.3 ,
             diagonalization = 'david' ,
 /
CELL_PARAMETERS alat 
     0.866025404    0.500000000    0.000000000 
     0.866025404   -0.500000000    0.000000000 
     0.000000000    0.000000000    5.400000000 
ATOMIC_SPECIES
   Ag  107.8682  Ag.pbe-n-kjpaw_psl.1.0.0.UPF 
    O   15.99940  O.pbe-n-kjpaw_psl.1.0.0.UPF 
    H    1.00800  H.pbe-kjpaw_psl.1.0.0.UPF 
ATOMIC_POSITIONS angstrom 
O        5.986597700   0.051902808  11.800640138
H        6.530086903   0.896034963  11.935550794
H        6.519207423  -0.788895855  11.940829013
O        2.800029893   0.013830142  11.748050047
H        3.756125095   0.022425916  11.956803063
Ag      -0.454154628   0.136836718   9.568098196
Ag       5.307442766   0.123896111   9.577760992
Ag       2.445911493   0.129358587   9.587754292
Ag       2.920157088   1.499919274   7.139192063
Ag       1.485120252  -0.981971793   7.160426239
Ag       4.380244685  -0.987689704   7.134282475
Ag       2.889028971  -1.667975200   4.717759990    0   0   0
Ag       4.333537867   0.833997281   4.717759990    0   0   0
Ag       5.778055146  -1.667970358   4.717759990    0   0   0
Ag       0.000000000   0.000000000   2.358879995    0   0   0
Ag       5.778052352   0.000009682   2.358879995    0   0   0
Ag       2.889026176   0.000004841   2.358879995    0   0   0
Ag       2.889023381   1.667984881   0.000000000    0   0   0
Ag       1.444514485  -0.833987600   0.000000000    0   0   0
Ag       4.333540661  -0.833982759   0.000000000    0   0   0   
K_POINTS automatic 
  4 4 1   0 0 0 


phonons at Gamma
 &inputph
  tr2_ph=1.0d-14,
  prefix='sym',
  alpha_mix=0.1,
  fildyn='phG.dyn',
  amass(3)=107.8682,
  amass(1)=15.999,
  amass(2)=1.0079,
  outdir='./'
  nat_todo=5,
 /
0.0 0.0 0.0
1 2 3 4 5





Au111.SCF input


 &CONTROL
                 calculation = 'scf' ,
                restart_mode = 'from_scratch' ,
                      outdir = './' ,
                  pseudo_dir = '/home/jibiaoli/pseudo/' ,
                      prefix = 'sym' ,
                     tstress = .true. ,
                     tprnfor = .true. ,
 /
 &SYSTEM
                       ibrav = 0,
                   celldm(1) = 9.438996782,
                         nat = 20,
                        ntyp = 3,
                     ecutwfc = 49 ,
                     ecutrho = 411 ,
                 occupations = 'smearing' ,
                     degauss = 0.02 ,
                    smearing = 'methfessel-paxton' ,
                    vdw_corr = 'DFT-D',
 /
 &ELECTRONS
                 mixing_beta = 0.3 ,
             diagonalization = 'david' ,
 /
CELL_PARAMETERS alat 
     0.866025404    0.500000000    0.000000000 
     0.866025404   -0.500000000    0.000000000 
     0.000000000    0.000000000    5.400000000 
ATOMIC_SPECIES
   Au  196.966  Au.pbe-n-kjpaw_psl.1.0.0.UPF 
    O   15.99940  O.pbe-n-kjpaw_psl.1.0.0.UPF 
    H    1.00800  H.pbe-kjpaw_psl.1.0.0.UPF 
ATOMIC_POSITIONS angstrom 
O        5.912480742   0.009178221  11.632181430
H        6.464419524   0.843711872  11.746544250
H        6.463965595  -0.824906263  11.746208129
O        2.776101640   0.006280334  11.529141825
H        3.735828757   0.004486229  11.732591760
Au      -0.212193475   0.013514349   9.300103694
Au       5.522293374   0.005423066   9.291997619
Au       2.653858209   0.011159754   9.350961280
Au       2.820570847   1.652453082   6.986020697
Au       1.396774134  -0.827316157   6.994544598
Au       4.265011175  -0.828154887   6.977373986
Au       2.883796376  -1.664954171   4.709215206    0   0   0
Au       4.325688984   0.832486750   4.709215206    0   0   0
Au       5.767589961  -1.664949338   4.709215206    0   0   0
Au       0.000000000   0.000000000   2.354607603    0   0   0
Au       5.767587172   0.000009664   2.354607603    0   0   0
Au       2.883793585   0.000004832   2.354607603    0   0   0
Au       2.883790796   1.664963835   0.000000000    0   0   0
Au       1.441898188  -0.832477085   0.000000000    0   0   0
Au       4.325691773  -0.832472253   0.000000000    0   0   0
K_POINTS automatic 
  4 4 1   0 0 0 


phonons at Gamma
 &inputph
  tr2_ph=1.0d-14,
  prefix='sym',
  alpha_mix=0.1,
  fildyn='phG.dyn',
  amass(1)=196.966,
  amass(2)=15.999,
  amass(3)=1.0079,
  outdir='./'
  nat_todo=5,
 /
0.0 0.0 0.0
1 2 3 4 5


------------------
Dr. Jibiao Li, 
Department of Material Science and Engineering
Yangtze Normal University
Juxian Dadao 16#, Fuling, Chongqing, China
Email: jibiaoli at yznu.edu.cn, jibiaoli at foxmail.com, jibiao.li at hotmail.com
Homepage: https://www.researchgate.net/profile/Jibiao_Li
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