[molpro-user] isotope vibrational frequencies

Kirk Peterson kipeters at wsu.edu
Tue Dec 9 16:32:28 GMT 2008


Jeremy,

ummm, this seems like a bit of a bug.  The only way I could get the  
2nd frequency job to accept the new masses was to restart the  
calculation from file 2:

***,HCl
memory,100,M
FILE,2,HCl.WFU
gprint,distance=1,angle=1
geometry={X,Y,ANGSTROM
H,
Cl, H, R1}
R1 = 1.27
basis=VDZ
! mass,iso,H=2.0141018,Cl=34.96885271
! {HF}
! {OPTG}
! {Frequencies}
  mass,iso,H=1.00794,Cl=34.96885271
  {Frequencies}


-Kirk

On Dec 9, 2008, at 6:57 AM, Jeremy Merritt wrote:

> Dr. Peterson,
> Thankyou for your reply.  However this still doesn't fully work for  
> me.  My output file is below.  The calculation does correctly  
> redefine the mass for the 1st freq. calculation, but then I get the  
> same answer for the second freq. calc.  I even tried to recalculate  
> the hessian with {frequencies,new} for the second freq. calc and it  
> still gives the vibrational freq. of DCl.
>
> Any suggestions?
> Thanks,
> Jeremy
>
>
> ***,HCl
> FILE,2,HCl.WFU,NEW
> memory,200,M
> gprint,distance=1,angle=1
> geometry={X,Y,ANGSTROM
> H,
> Cl, H, R1}
> R1 = 1.27
> basis=VDZ
>  mass,iso,H=2.0141018,Cl=34.96885271
>  {HF}
>  {OPTG}
>  {Frequencies}
>  mass,iso,H=1.00794,Cl=34.96885271
>  {Frequencies}
>
> Variables initialized (599), CPU time= 0.01 sec
> Commands  initialized (355), CPU time= 0.02 sec, 460 directives.
> Default parameters read. Elapsed time= 0.09 sec
> Checking input...
> Passed
> 1
>
>
>                                        ***  PROGRAM SYSTEM MOLPRO  ***
>                        Copyright, University College Cardiff  
> Consultants Limited, 2004
>
>                                   Version 2008.1 linked 25 Aug 2008  
> 15:17:21
>
>
> **********************************************************************************************************************************
> LABEL *   HCl
> Linux-2.6.4-52-smp/f23(x86_64) 64 bit  
> version                                           DATE:   9- 
> Dec-08         TIME: 09:18:52  
> **********************************************************************************************************************************
>
> Patch level:      3
> **********************************************************************************************************************************
>
> Variable memory set to    8000000 words,  buffer space   230000 words
>
>
>
> Permanent file  2  hcl.wfu  assigned.  Implementation=df
>
>
> **********************************************************************************************************************************
> DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
>             2       1        0.03        
> 500                                           VAR
> PROGRAMS   *        TOTAL      FILE
> CPU TIMES  *         0.28      0.00
> REAL TIME  *         0.34 SEC
> DISK USED  *         0.03 MB      
> **********************************************************************************************************************************
>
> SETTING R1             =         1.27000000
> Variable memory set to  200000000 words,  buffer space   230000 words
>
> SETTING BASIS          =    VDZ
>
> SETTING MASS FOR H    (Z=  1)   TO   2.014
> SETTING MASS FOR CL   (Z= 17)   TO  34.969
>
>
> Recomputing integrals since basis changed
>
>
> Using spherical harmonics
>
> Library entry H      S cc-pVDZ              selected for orbital  
> group  1
> Library entry H      P cc-pVDZ              selected for orbital  
> group  1
> Library entry CL     S cc-pVDZ              selected for orbital  
> group  2
> Library entry CL     P cc-pVDZ              selected for orbital  
> group  2
> Library entry CL     D cc-pVDZ              selected for orbital  
> group  2
>
> 1PROGRAM * SEWARD (Integral evaluation for generally contracted  
> gaussian basis sets)     Author: Roland Lindh, 1990
>
> Geometry written to block  1 of record 700
>
> Orientation using atomic masses Molecule type: Linear
> User-specified symmetry elements: X,Y
> Symmetry elements: X,Y
> Rotational constants:     164.5313064    164.5313064      0.0000000  
> GHz
>
> Point group  C2v
>
>
>
> ATOMIC COORDINATES
>
> NR  ATOM    CHARGE       X              Y              Z
>
>  1  H       1.00    0.000000000    0.000000000   -2.269250136
>  2  CL     17.00    0.000000000    0.000000000    0.130702051
>
> Bond lengths in Bohr (Angstrom)
>
> 1-2  2.399952187
>    (1.270000000)
>
> NUCLEAR CHARGE:                   18
> NUMBER OF PRIMITIVE AOS:          49
> NUMBER OF SYMMETRY AOS:           48
> NUMBER OF CONTRACTIONS:           23   (  12A1  +   5B1  +   5B2   
> +   1A2  )
> NUMBER OF CORE ORBITALS:           5   (   3A1  +   1B1  +   1B2   
> +   0A2  )
> NUMBER OF VALENCE ORBITALS:        5   (   3A1  +   1B1  +   1B2   
> +   0A2  )
>
>
> NUCLEAR REPULSION ENERGY    7.08347445
>
> EXTRA SYMMETRY OF AOS IN SYMMETRY 1:   1 1 1 1 1 1 1 1 1 1   1 2
>
> Eigenvalues of metric
>
>        1 0.209E-01 0.656E-01 0.103E+00 0.165E+00 0.927E+00 0.100E+01  
> 0.100E+01 0.100E+01
>        2 0.124E+00 0.651E+00 0.100E+01 0.123E+01 0.199E+01
>        3 0.124E+00 0.651E+00 0.100E+01 0.123E+01 0.199E+01
>        4 0.100E+01
>
>
> Contracted 2-electron integrals neglected if value below      1.0D-11
> AO integral compression algorithm  1   Integral accuracy      1.0D-11
>
>    0.262 MB (compressed) written to integral file (100.0%)
>
>
> NUMBER OF SORTED TWO-ELECTRON INTEGRALS:      12241.     BUFFER  
> LENGTH:  32768
> NUMBER OF SEGMENTS:   1  SEGMENT LENGTH:      12241      RECORD  
> LENGTH: 524288
>
> Memory used in sort:       0.57 MW
>
> SORT1 READ       16495. AND WROTE        9376. INTEGRALS IN      1  
> RECORDS. CPU TIME:     0.00 SEC, REAL TIME:     0.01 SEC
> SORT2 READ        9376. AND WROTE       12241. INTEGRALS IN      1  
> RECORDS. CPU TIME:     0.00 SEC, REAL TIME:     0.02 SEC
>
> FILE SIZES:   FILE 1:     2.3 MBYTE,  FILE 4:     4.2 MBYTE,    
> TOTAL:      6.6 MBYTE
>
> OPERATOR DM      FOR CENTER  0  COORDINATES:    0.000000     
> 0.000000    0.000000
>
>
> **********************************************************************************************************************************
> DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
>             1      19        2.13       500      610      700       
> 900      950      970     1000      129      960      
> 1100                                           VAR    BASINP     
> GEOM    SYMINP    ZMAT    AOBASIS   BASIS     P2S    ABASIS      S
>                                        1400     1410     1200      
> 1210     1080     1600     1650     1300      
> 1700                                            T        V        
> H0       H01     AOSYM     SMH    MOLCAS    ERIS     OPER
>             2       4        1.11       500      610      700      
> 1000                                           VAR    BASINP     
> GEOM     BASIS
> PROGRAMS   *        TOTAL       INT      FILE
> CPU TIMES  *         0.40      0.09      0.00
> REAL TIME  *         0.53 SEC
> DISK USED  *         7.90 MB      
> **********************************************************************************************************************************
>
> 1PROGRAM * RHF-SCF (CLOSED SHELL)       Authors: W. Meyer, H.-J.  
> Werner
>
>
> NUMBER OF ELECTRONS:       9+    9-
> CONVERGENCE THRESHOLDS:    1.00E-06 (Density)    1.00E-07 (Energy)
> MAX. NUMBER OF ITERATIONS:       60
> INTERPOLATION TYPE:            DIIS
> INTERPOLATION STEPS:              2 (START)      1 (STEP)
> LEVEL SHIFTS:                  0.00 (CLOSED)  0.00 (OPEN)
>
>
>
> Orbital guess generated from atomic densities.  Occupancy:    6    
> 2   2   0
>
> Molecular orbital dump at record        2100.2
>
> ITERATION    DDIFF          GRAD             ENERGY        2- 
> EL.EN.            DIPOLE MOMENTS         DIIS
>   1      0.000D+00      0.000D+00      -460.07344612    366.700881    
> 0.000000   0.000000  -0.981778    0
>   2      0.000D+00      0.195D-01      -460.08804901    365.127719    
> 0.000000   0.000000  -0.501179    1
>   3      0.478D-01      0.619D-02      -460.08927421    365.611507    
> 0.000000   0.000000  -0.575282    2
>   4      0.909D-02      0.141D-02      -460.08940947    365.565954    
> 0.000000   0.000000  -0.558117    3
>   5      0.327D-02      0.277D-03      -460.08941449    365.576206    
> 0.000000   0.000000  -0.555003    4
>   6      0.611D-03      0.412D-04      -460.08941458    365.572539    
> 0.000000   0.000000  -0.554803    5
>   7      0.858D-04      0.930D-05      -460.08941459    365.573051    
> 0.000000   0.000000  -0.554676    6
>   8      0.321D-04      0.106D-05      -460.08941459    365.573013    
> 0.000000   0.000000  -0.554658    6
>   9      0.319D-05      0.191D-06      -460.08941459    365.573014    
> 0.000000   0.000000  -0.554655    5
>  10      0.639D-06      0.125D-07      -460.08941459    365.573014    
> 0.000000   0.000000  -0.554654    0
>
> Final occupancy:   5   2   2   0
>
> !RHF STATE 1.1 Energy               -460.089414586984
> Nuclear energy                         7.08347445
> One-electron energy                 -649.95939593
> Two-electron energy                  182.78650689
> Virial quotient                       -0.99998596
> !RHF STATE 1.1 Dipole moment           0.00000000     0.00000000     
> -0.55465432
> Dipole moment /Debye                   0.00000000     0.00000000     
> -1.40969832
>
> Orbital energies:
>
>        1.1          2.1          3.1          4.1           
> 5.1          6.1          7.1
>  -104.843011   -10.568600    -8.036591    -1.114522    -0.621678      
> 0.150193     0.494246
>
>        1.2          2.2          3.2          4.2
>    -8.032814    -0.471580     0.750907     0.879037
>
>        1.3          2.3          3.3          4.3
>    -8.032814    -0.471580     0.750907     0.879037
>
>        1.4
>     0.981016
>
>
> **********************************************************************************************************************************
> DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
>             1      19        2.13       500      610      700       
> 900      950      970     1000      129      960      
> 1100                                           VAR    BASINP     
> GEOM    SYMINP    ZMAT    AOBASIS   BASIS     P2S    ABASIS      S
>                                        1400     1410     1200      
> 1210     1080     1600     1650     1300      
> 1700                                            T        V        
> H0       H01     AOSYM     SMH    MOLCAS    ERIS     OPER
>             2       5        1.14       500      610      700      
> 1000     2100                                           VAR     
> BASINP    GEOM     BASIS     RHF
> PROGRAMS   *        TOTAL        HF       INT      FILE
> CPU TIMES  *         0.42      0.01      0.09      0.00
> REAL TIME  *         0.58 SEC
> DISK USED  *         7.90 MB      
> **********************************************************************************************************************************
>
>
> PROGRAM * OPT (Geometry optimization)     Authors: F. Eckert and H.- 
> J. Werner
>
>
> *** Long output written to logfile /fire/heaven/merrit/MOLPOOL/BeOBe/ 
> BeOBe-iso.log ***
>
>
> Geometry optimization using default procedure for command HF-SCF
>
> Geometry written to block  1 of record 700
>
> Making model hessian for Z-matrix coordinates
>
> Quadratic Steepest Descent - Minimum Search
>
> Optimization point 1
>
> Variable                      Last           Current         
> Next           Gradient       Hessian
>
> E(HF-SCF000) / Hartree      0.00000000  -460.08941459     0.00000000
> R1 / ANGSTROM               0.00000000     1.27000000      
> 1.27471876    -0.00976772     2.06997840
> Convergence:                0.00000000  (line search)      
> 0.00891716     0.00516886  (total)
>
> Optimization point 2
>
> Variable                      Last           Current         
> Next           Gradient       Hessian
>
> E(HF-SCF000) / Hartree   -460.08941459  -460.08944561     0.00000000
> R1 / ANGSTROM               1.27000000     1.27471876      
> 1.27724501    -0.00340590     1.34820007
> Convergence:                0.00000000  (line search)      
> 0.00477393     0.00180232  (total)
>
> Optimization point 3
>
> Variable                      Last           Current         
> Next           Gradient       Hessian
>
> E(HF-SCF000) / Hartree   -460.08944561  -460.08944998     0.00000000
> R1 / ANGSTROM               1.27471876     1.27724501      
> 1.27729469    -0.00006569     1.32219818
> Convergence:                0.00000000  (line search)      
> 0.00009388     0.00003476  (total)
>
> END OF GEOMETRY OPTIMIZATION.    TOTAL CPU:         7.3 SEC
>
> ITER.   ENERGY(OLD)    ENERGY(NEW)      DE          GRADMAX      
> GRADNORM    GRADRMS     STEPMAX     STEPLEN     STEPRMS
>  1  -460.08941459  -460.08944561    -0.00003102  0.00516886   
> 0.00516886  0.00516886  0.00891716  0.00891716  0.00891716
>  2  -460.08944561  -460.08944998    -0.00000438  0.00180232   
> 0.00180232  0.00180232  0.00477393  0.00477393  0.00477393
>  3  -460.08944998  -460.08944998     0.00000000  0.00003476   
> 0.00003476  0.00003476  0.00009388  0.00009388  0.00009388
>
> Geometry written to block  1 of record 700
>
>
> **********************************************************************************************************************************
> DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
>             1      19        2.13       500      610      700       
> 900      950      970     1000      129      960      
> 1100                                           VAR    BASINP     
> GEOM    SYMINP    ZMAT    AOBASIS   BASIS     P2S    ABASIS      S
>                                        1400     1410     1200      
> 1210     1080     1600     1650     1300      
> 1700                                            T        V        
> H0       H01     AOSYM     SMH    MOLCAS    ERIS     OPER
>             2       5        1.14       500      610      700      
> 1000     2100                                           VAR     
> BASINP    GEOM     BASIS     RHF
> PROGRAMS   *        TOTAL      OPTG        HF       INT      FILE
> CPU TIMES  *         7.69      7.26      0.01      0.09      0.00
> REAL TIME  *         9.44 SEC
> DISK USED  *         7.93 MB      
> **********************************************************************************************************************************
>
>
> PROGRAM * HESSIAN
>
> Computing numerical hessian using default procedure for command HF-SCF
>
> Symmetry elements for unique displacements: X  Y
> Using no symmetry in wavefunction calculations
>
> Running default procedure: HF-SCF000
>
>
> Numerically approximating hessian using central gradient differences
>
> Task list generated. Total number of displacements:      8
>
>   5 tasks completed, CPU=    12.54 sec, Elapsed=    13.78 sec
>
> Numerical HF-SCF000 hessian completed. CPU-time:    20.08 sec,  
> Elapsed:    21.46 sec
>
> HF-SCF hessian saved to record  5300.2
>
> FREQUENCIES * CALCULATION OF HARMONIC VIBRATIONAL SPECTRA FOR HF-SCF
>
>
> Permanent Dipole Moment [debye]
>  1-  3    0.000000    0.000000   -1.417564
>
> Dipole Moment Norm    1.4175641 [debye]
>
> Dipole Moment Derivatives [debye/ang]
>                  1             2             3              
> 4             5             6
>        1     1.1098250     0.0000000     0.0000000    -1.1098210      
> 0.0000000     0.0000000
>        2     0.0000000     1.1098250     0.0000000     0.0000000     
> -1.1098210     0.0000000
>        3     0.0000000     0.0000000     1.0777493     0.0000000      
> 0.0000000    -1.0777532
>
> Projecting out rotations and translations
>
>  Low Vibration      Wavenumber
>       Nr             [1/cm]
>       1                0.00
>       2                0.00
>       3                0.00
>       4                0.00
>       5                0.00
>
>    Vibration        Wavenumber
>       Nr             [1/cm]
>       1             2258.72
>
> FREQUENCIES * CALCULATION OF NORMAL MODES FOR HF-SCF
>
>
> Atomic Coordinates
>
> Nr  Atom  Charge       X              Y              Z
>
>  1   H     1.00    0.000000000    0.000000000   -2.282284369
>  2   CL   17.00    0.000000000    0.000000000    0.131452784
>
> Frequencies dumped to record   5400.2
>
> Gradient norm at reference geometry: 0.65687D-04
>
> Normal Modes
>
>                             1 A1
> Wavenumbers [cm-1]         2258.72
> Intensities [km/mol]         25.78
> Intensities [relative]      100.00
>          HX1              0.00000
>          HY1              0.00000
>          HZ1              0.68517
>          CLX2             0.00000
>          CLY2             0.00000
>          CLZ2            -0.03946
>
>
> Normal Modes of low/zero frequencies
>
>                                 1           2           3            
> 4           5
> Wavenumbers [cm-1]            0.00        0.00        0.00         
> 0.00        0.00
> Intensities [km/mol]          0.00        0.00        0.00         
> 0.00        0.00
> Intensities [relative]        0.00        0.00        0.00         
> 0.00        0.00
>          HX1              0.00000     0.00000    -0.07488      
> 0.70064     0.00000
>          HY1              0.67032     0.00000     0.00000      
> 0.00000     0.21718
>          HZ1             -0.05068     0.00000     0.00000      
> 0.00000     0.15643
>          CLX2             0.00000    -0.00015     0.16815      
> 0.01797     0.00000
>          CLY2             0.00000     0.16911     0.00014      
> 0.00002     0.00000
>          CLZ2            -0.05068     0.00000     0.00000      
> 0.00000     0.15643
>
>
> Zero point energy:  0.00514573 [H]     1129.36 [1/CM]       13.51  
> [KJ/MOL]
> Frequency information read from record  5400.2
>
> Recomputing wavefunction at initial geometry
>
>
> **********************************************************************************************************************************
> DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
>             1      19        2.13       500      610      700       
> 900      950      970     1000      129      960      
> 1100                                           VAR    BASINP     
> GEOM    SYMINP    ZMAT    AOBASIS   BASIS     P2S    ABASIS      S
>                                        1400     1410     1200      
> 1210     1080     1600     1650     1300      
> 1700                                            T        V        
> H0       H01     AOSYM     SMH    MOLCAS    ERIS     OPER
>             2       8        1.15       500      610      700      
> 1000     2100     5300     5400      
> 5450                                           VAR    BASINP     
> GEOM     BASIS     RHF     HESS     FREQ     NMOD
> PROGRAMS   *        TOTAL      FREQ      OPTG        HF        
> INT      FILE
> CPU TIMES  *        27.64     19.93      7.26      0.01       
> 0.09      0.00
> REAL TIME  *        31.13 SEC
> DISK USED  *         9.16 MB      
> **********************************************************************************************************************************
>
> SETTING MASS FOR H    (Z=  1)   TO   1.008
> SETTING MASS FOR CL   (Z= 17)   TO  34.969
>
>
> PROGRAM * HESSIAN
>
> HF-SCF hessian read from record  5300.2
>
> FREQUENCIES * CALCULATION OF HARMONIC VIBRATIONAL SPECTRA FOR HF-SCF
>
>
> Permanent Dipole Moment [debye]
>  1-  3    0.000000    0.000000   -1.417564
>
> Dipole Moment Norm    1.4175641 [debye]
>
> Dipole Moment Derivatives [debye/ang]
>                  1             2             3              
> 4             5             6
>        1     1.1098250     0.0000000     0.0000000    -1.1098210      
> 0.0000000     0.0000000
>        2     0.0000000     1.1098250     0.0000000     0.0000000     
> -1.1098210     0.0000000
>        3     0.0000000     0.0000000     1.0777493     0.0000000      
> 0.0000000    -1.0777532
>
> Projecting out rotations and translations
>
>  Low Vibration      Wavenumber
>       Nr             [1/cm]
>       1                0.00
>       2                0.00
>       3                0.00
>       4                0.00
>       5                0.00
>
>    Vibration        Wavenumber
>       Nr             [1/cm]
>       1             2258.72
>
> FREQUENCIES * CALCULATION OF NORMAL MODES FOR HF-SCF
>
>
> Atomic Coordinates
>
> Nr  Atom  Charge       X              Y              Z
>
>  1   H     1.00    0.000000000    0.000000000   -2.282284369
>  2   CL   17.00    0.000000000    0.000000000    0.131452784
>
> Frequencies dumped to record   5401.2
>
> Gradient norm at reference geometry: 0.65687D-04
>
> Normal Modes
>
>                             1 A1
> Wavenumbers [cm-1]         2258.72
> Intensities [km/mol]         25.78
> Intensities [relative]      100.00
>          HX1A             0.00000
>          HY1A             0.00000
>          HZ1A             0.68517
>          CLX2A            0.00000
>          CLY2A            0.00000
>          CLZ2A           -0.03946
>
>
> Normal Modes of low/zero frequencies
>
>                                 1           2           3            
> 4           5
> Wavenumbers [cm-1]            0.00        0.00        0.00         
> 0.00        0.00
> Intensities [km/mol]          0.00        0.00        0.00         
> 0.00        0.00
> Intensities [relative]        0.00        0.00        0.00         
> 0.00        0.00
>          HX1A             0.00000     0.00000    -0.07488      
> 0.70064     0.00000
>          HY1A             0.67032     0.00000     0.00000      
> 0.00000     0.21718
>          HZ1A            -0.05068     0.00000     0.00000      
> 0.00000     0.15643
>          CLX2A            0.00000    -0.00015     0.16815      
> 0.01797     0.00000
>          CLY2A            0.00000     0.16911     0.00014      
> 0.00002     0.00000
>          CLZ2A           -0.05068     0.00000     0.00000      
> 0.00000     0.15643
>
>
> Zero point energy:  0.00514573 [H]     1129.36 [1/CM]       13.51  
> [KJ/MOL]
> Frequency information read from record  5401.2
>
>
> **********************************************************************************************************************************
> DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
>             1      20        2.14       500      610      700       
> 900      950      970     1000      129      960      
> 1100                                           VAR    BASINP     
> GEOM    SYMINP    ZMAT    AOBASIS   BASIS     P2S    ABASIS      S
>                                        1400     1410     1200      
> 1210     1080     1600     1650     1300     1700       
> 701                                            T        V        
> H0       H01     AOSYM     SMH    MOLCAS    ERIS     OPER     GEOM
>             2      11        1.35       500      610      700      
> 1000     2100     5300     5400     5450      701      
> 5401                                           VAR    BASINP     
> GEOM     BASIS     RHF     HESS     FREQ     NMOD     GEOM      
> FREQ                                           
> 5451                                          NMOD
> PROGRAMS   *        TOTAL      FREQ      FREQ      OPTG         
> HF       INT      FILE
> CPU TIMES  *        27.67      0.01     19.93      7.26       
> 0.01      0.09      0.00
> REAL TIME  *        31.18 SEC
> DISK USED  *         9.16 MB      
> **********************************************************************************************************************************
>
>       OPTG(HF)        HF-SCF   -460.08944998   -460.08941459
> **********************************************************************************************************************************
>
> -- 
> Jeremy Merritt, PhD
> Department of Chemistry
> CB 212 Atwood Hall
> Emory University
> Atlanta, Ga 30322
> Voice: 404-727-0029
> Fax: 404-727-6586
> Email: jeremy.merritt at emory.edu
>




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