Nonlinear Optics - Time Dependent Hartree-Fock

  • In MOPAC2012, it is possible to perform calculations of the first and second static hyperpolarizabilities, as well as of other nonlinear optical properties of a lanthanide complex, by using the POLAR keyword.
     
  • As an example, let us consider the complex LOWBEE: [(1,10-(1,1'-Dimethylene-3,3'-biisoquinoline-2,2'-dioxide)-4,7,13,16-tetraoxa-1,10-diazaoctadecaphane)-(trifluoromethanesulfonato-O,O')-europium(iii)], below:
    lowbee ccsd
     
  • First you must draw the structure of your complex and prepare a MOPAC2012 input data file. For that purpose, please follow the Drawing Complexes tutorial.
    • In the Drawing Complexes tutorial, instead of step 5 of the Optimize the geometry of the lanthanide complex with MOPAC2012 do the following: in the field “Additional keywords”, replace GNORM=0.01 by GNORM=0.25, add SPARKLE, and add POLAR(E=(0.0)), as such: GNORM=0.25 SPARKLE POLAR(E=(0.0)).
       
    • Finish the Drawing Complexes tutorial. As an example, we provide the MOPAC2012 input file lowbee.mop.
  • The nonlinear optics results are presented in the end of the MOPAC2012 .out file, as shown below: 
    			
 ******************** TDHF POLARIZABILITIES ********************




 ENERGY OF "REORIENTED" SYSTEM WITHOUT FIELD:      103.7009259626


  NFREQ=  1  IWFLB=  0  IBET=  1  IGAM=  1
  ATOL= 0.10000D-02  BTOL= 0.10000D-02    MAXITU=  500    MAXITA=  150


 *****************************************************************
 CALCULATION OF STATIC FIELD QUANTITIES
 *****************************************************************

 +++++ ALPHA AT       0.00000 EV.

                           COMPONENTS OF ALPHA

                     *X           *Y           *Z
           *=X:     490.7466      70.1518     -64.4160
           *=Y:      70.1518     457.4762      94.8438
           *=Z:     -64.4138      94.8407     543.4913

  ISOTROPIC AVERAGE ALPHA =     497.23805 A.U. =     73.68308 ANG.**3

 +++++ BETA (SECOND HARMONIC GENERATION) AT       0.00000 EV.

                              COMPONENTS OF BETA
            *XX         *XY         *YY         *XZ         *YZ         *ZZ
   *=X  -418.45256    57.73681    -3.66392  -129.64914    56.17695   226.10560
   *=Y    57.76086    -3.70124    66.35581    56.09767   122.54567   121.59046
   *=Z  -129.63230    56.12991   122.53061   226.08379   121.57058     5.49809


 AVERAGE BETAX(SHG) VALUE AT   0.00000 EV =       -117.6302 a.u. = -0.101626E-29 ESU
 AVERAGE BETAY(SHG) VALUE AT   0.00000 EV =        147.4067 a.u. =  0.127351E-29 ESU
 AVERAGE BETAZ(SHG) VALUE AT   0.00000 EV =         -0.9629 a.u. = -0.831866E-32 ESU



 AVERAGE BETA (SHG) VALUE AT   0.00000 EV =        188.5909 a.u. =  0.162932E-29 ESU
   (1 a.u. = 8.639418X10-33 esu)



 +++++ ALPHA AT       0.00000 EV.

                           COMPONENTS OF ALPHA

                     *X           *Y           *Z
           *=X:     490.7466      70.1518     -64.4160
           *=Y:      70.1518     457.4762      94.8438
           *=Z:     -64.4138      94.8407     543.4913

  ISOTROPIC AVERAGE ALPHA =     497.23805 A.U. =     73.68308 ANG.**3


 GAMMA (THIRD HARMONIC GENERATION) AT    0.00000 EV.


 GAMMA(X,X,X,X) =         65367.73738
 GAMMA(Y,Y,Y,Y) =         39838.07460
 GAMMA(Z,Z,Z,Z) =        269371.79491
 GAMMA(X,X,Y,Y) =         18570.97627
 GAMMA(X,X,Z,Z) =         40182.46797
 GAMMA(Y,Y,X,X) =         18570.97651
 GAMMA(Y,Y,Z,Z) =         54604.78176
 GAMMA(Z,Z,X,X) =         40182.47118
 GAMMA(Z,Z,Y,Y) =         54604.78627


 AVERAGE GAMMA VALUE AT    0.00000 =        120258.81337 a.u. =        60570.78755 ESU (X10-39)





 TOTAL CPU TIME:           507.08 SECONDS

 == MOPAC DONE ==
  • For convenience, we provide the MOPAC2012 output file lowbee.out.
  • You can specify the energies of the radiation to be used in eV with the E=(n) option. For example, if instead of the static values for these properties, E=(0.0), you want to compute them for a 0.25eV laser source, simply specify: POLAR(E=(0.25)).
     
  • Further nonlinear optical properties of lanthanide complexes can also be computed by selecting additional keywords. Example, for a 1.0eV laser source, use the following keywords to compute:
    • Second Harmonic Generation: POLAR(E=(1.0), IWFLB=1)
       
    • Noniterative calculation of Second Harmonic Generation: POLAR(E=(1.0), BETA=-1)
       
    • Electrooptical Pockels Effect: POLAR(E=(1.0), IWFLB=2)
       
    • Noniterative calculation of Electrooptical Pockels Effect: POLAR(E=(1.0),BETA=-2)
       
    • Optical Rectification: POLAR(E=(1.0), IWFLB=3)
       
    • Noniterative calculation of Optical Rectification: POLAR(E=(1.0), BETA=-3)
       
    • Third Harmonic Generation: POLAR(E=(1.0), GAMMA=1)
       
    • DC-EFISH: POLAR(E=(1.0), GAMMA=2)
       
    • Intensity Dependent Index of Refraction: POLAR(E=(1.0), GAMMA=3)
       
    • Optical Kerr Effect: POLAR(E=(1.0), GAMMA=4)
       
  • For more information on these keywords, refer to "Time-Dependent Hartree-Fock" on the MOPAC2012 manual.