#!/bin/sh # ============================================================================================== # # Charge Separation Calculation of a ethylene dimer: # C2H4* + C2H4 --> C2H4+ + C2H4- # aimed at: # # 1) calculate site energies and couplings of fde-derived of a localized exciton # (Diabat 1) and charge-separated state (Diabat 2). The exciton is obtained by using # XCDFT method. # # 2) calculate the charge-transfer excitation energy from a two-state model that # includes the two charge-localized states involved in the calculation # # First the isolated (restricted) neutral fragments are obtained. Symmetry NOSYM is used. # In addition, an isolated unrestricted neutral calculation of the fragment to be excited is performed. # Resulting files: t21.iso.rho1, t21.iso.rho2 and gs.t21. Next in the first FDE calculation: # state C2H4* (neutral-XCDFT excitation) and C2H4(neutral), resulting files: # fragA1.t21 and fragA2.t21. The freeze and thaw cycles are done manually since # open-shell fragments were used. Next in the second FDE calculation: state C2H4+ and C2H4-, # resulting files fragB1.t21 and fragB2.t21. Again freeze and thaw cycles are done manually since # open-shell fragments were used. # # In the final charge separation calculation the ELECTRONTRANSFER block keyword is used. # The files fragA1.t21, fragA2.t21, fragB1.t21, and fragB2.t21 must exist and must have these names. # =================================================================================================== # ================================================== # OBTAIN ISOLATED FRAGMENTS # ================================================== $ADFBIN/adf << eor Title MODCO: Fragment no. 1; (isolated) EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END ATOMS H 0.930241 1.239503 0.000000 H -0.930241 1.239503 0.000000 C 0.000000 0.667450 0.000000 C 0.000000 -0.667450 0.000000 H 0.930241 -1.239503 0.000000 H -0.930241 -1.239503 0.000000 END BASIS Type TZP Core None END eor rm logfile mv TAPE21 t21.iso.rho1 $ADFBIN/adf << eor Title MODCO: Fragment no. 2; (isolated) EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END ATOMS H 0.930241 1.239503 8.000000 H -0.930241 1.239503 8.000000 C 0.000000 0.667450 8.000000 C 0.000000 -0.667450 8.000000 H 0.930241 -1.239503 8.000000 H -0.930241 -1.239503 8.000000 END BASIS Type TZP Core None END eor rm logfile mv TAPE21 t21.iso.rho2 # ================================================== # OBTAIN ISOLATED UNRESTRICTED FRAGMENT # ================================================== $ADFBIN/adf << eor Title Fragment 1; (isolated_unrestricted) EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END CHARGE 0 0 UNRESTRICTED ATOMS H 0.930241 1.239503 0.000000 H -0.930241 1.239503 0.000000 C 0.000000 0.667450 0.000000 C 0.000000 -0.667450 0.000000 H 0.930241 -1.239503 0.000000 H -0.930241 -1.239503 0.000000 END BASIS Type TZP Core None END eor rm logfile # ================================================== # RENAME TAPE21 file as gs.t21, as required in # XCDFT methodology. # ================================================== mv TAPE21 gs.t21 # ================================================== # FIRST FDE CALCULATION: STATE D* (XCDFT) + A # note: the freeze and thaw is done manually # as we have open-shell fragments # ================================================== $ADFBIN/adf << eor Title MODCO: Fragment no. 1; (polarized) EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END CDFT MAXITER 250 NCONSTRAINTS 1 EXCITEDCDFT METRIC ALLATOMS NATOMSPERSET 36 CONSTRAINTS 1.0 INITIALMULTIPLIERS 0.0 THRESHOLD 1.0e-9 STEPSIZE 0.4 PRINT LOW END CHARGE 0 0 UNRESTRICTED FRAGMENTS rho1 t21.iso.rho1 rho2 t21.iso.rho2 type=fde END ATOMS H 0.930241 1.239503 0.000000 f=rho1 H -0.930241 1.239503 0.000000 f=rho1 C 0.000000 0.667450 0.000000 f=rho1 C 0.000000 -0.667450 0.000000 f=rho1 H 0.930241 -1.239503 0.000000 f=rho1 H -0.930241 -1.239503 0.000000 f=rho1 H 0.930241 1.239503 8.000000 f=rho2 H -0.930241 1.239503 8.000000 f=rho2 C 0.000000 0.667450 8.000000 f=rho2 C 0.000000 -0.667450 8.000000 f=rho2 H 0.930241 -1.239503 8.000000 f=rho2 H -0.930241 -1.239503 8.000000 f=rho2 END ALLOW PARTIALSUPERFRAGS FDE PW91K GGAPOTXFD pw91x GGAPOTCFD pw91c END eor rm logfile mv TAPE21 t21.emb.rho1 $ADFBIN/adf << eor Title MODCO: Fragment no. 2; (polarized) EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END CHARGE 0 0 UNRESTRICTED FRAGMENTS rho1 t21.emb.rho1 subfrag=active type=fde rho2 t21.iso.rho2 END ATOMS H 0.930241 1.239503 0.000000 f=rho1 H -0.930241 1.239503 0.000000 f=rho1 C 0.000000 0.667450 0.000000 f=rho1 C 0.000000 -0.667450 0.000000 f=rho1 H 0.930241 -1.239503 0.000000 f=rho1 H -0.930241 -1.239503 0.000000 f=rho1 H 0.930241 1.239503 8.000000 f=rho2 H -0.930241 1.239503 8.000000 f=rho2 C 0.000000 0.667450 8.000000 f=rho2 C 0.000000 -0.667450 8.000000 f=rho2 H 0.930241 -1.239503 8.000000 f=rho2 H -0.930241 -1.239503 8.000000 f=rho2 END ALLOW PARTIALSUPERFRAGS FDE PW91K GGAPOTXFD pw91x GGAPOTCFD pw91c END eor rm logfile mv TAPE21 t21.emb.rho2 it=1 while [ $it -le 2 ]; do $ADFBIN/adf << eor Title MODCO: Fragment no. 1; relaxed EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END NumericalQuality Good CDFT MAXITER 250 NCONSTRAINTS 1 EXCITEDCDFT METRIC ALLATOMS NATOMSPERSET 36 CONSTRAINTS 1.0 INITIALMULTIPLIERS 0.0 THRESHOLD 1.0e-9 STEPSIZE 0.4 PRINT LOW END CHARGE 0 0 UNRESTRICTED FRAGMENTS rho1 t21.iso.rho1 rho2 t21.emb.rho2 subfrag=active type=fde END restart file t21.emb.rho1 end ATOMS H 0.930241 1.239503 0.000000 f=rho1 H -0.930241 1.239503 0.000000 f=rho1 C 0.000000 0.667450 0.000000 f=rho1 C 0.000000 -0.667450 0.000000 f=rho1 H 0.930241 -1.239503 0.000000 f=rho1 H -0.930241 -1.239503 0.000000 f=rho1 H 0.930241 1.239503 8.000000 f=rho2 H -0.930241 1.239503 8.000000 f=rho2 C 0.000000 0.667450 8.000000 f=rho2 C 0.000000 -0.667450 8.000000 f=rho2 H 0.930241 -1.239503 8.000000 f=rho2 H -0.930241 -1.239503 8.000000 f=rho2 END ALLOW PARTIALSUPERFRAGS FDE PW91K GGAPOTXFD pw91x GGAPOTCFD pw91c FullGrid Energy END eor rm logfile mv TAPE21 t21.emb.rho1 $ADFBIN/adf << eor Title MODCO: Fragment no. 2; relaxed EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END NumericalQuality Good restart file t21.emb.rho2 end CHARGE 0 0 UNRESTRICTED FRAGMENTS rho1 t21.emb.rho1 subfrag=active type=fde rho2 t21.iso.rho2 END ATOMS H 0.930241 1.239503 0.000000 f=rho1 H -0.930241 1.239503 0.000000 f=rho1 C 0.000000 0.667450 0.000000 f=rho1 C 0.000000 -0.667450 0.000000 f=rho1 H 0.930241 -1.239503 0.000000 f=rho1 H -0.930241 -1.239503 0.000000 f=rho1 H 0.930241 1.239503 8.000000 f=rho2 H -0.930241 1.239503 8.000000 f=rho2 C 0.000000 0.667450 8.000000 f=rho2 C 0.000000 -0.667450 8.000000 f=rho2 H 0.930241 -1.239503 8.000000 f=rho2 H -0.930241 -1.239503 8.000000 f=rho2 END ALLOW PARTIALSUPERFRAGS FDE PW91K GGAPOTXFD pw91x GGAPOTCFD pw91c FullGrid Energy END eor rm logfile mv TAPE21 t21.emb.rho2 it=$(($it+1)) done # ====================================== # NOW THE TAPE21 FILES MUST BE RENAMED # # TO: fragA1.t21, fragA2.t21 # .... up to a max of fragA999.t21 # AND: fragB1.t21, fragB2.t21 # .... up to a max of fragB999.t21 # ====================================== mv t21.emb.rho1 fragA1.t21 mv t21.emb.rho2 fragA2.t21 # ================================================== # SECOND FDE CALCULATION: STATE D+ + A- # note: the freeze and thaw is done manually # as we have open-shell fragments # ================================================== $ADFBIN/adf << eor Title MODCO: Fragment no. 1; (polarized) EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END CHARGE 1 -1 UNRESTRICTED FRAGMENTS rho1 t21.iso.rho1 rho2 t21.iso.rho2 type=fde END ATOMS H 0.930241 1.239503 0.000000 f=rho1 H -0.930241 1.239503 0.000000 f=rho1 C 0.000000 0.667450 0.000000 f=rho1 C 0.000000 -0.667450 0.000000 f=rho1 H 0.930241 -1.239503 0.000000 f=rho1 H -0.930241 -1.239503 0.000000 f=rho1 H 0.930241 1.239503 8.000000 f=rho2 H -0.930241 1.239503 8.000000 f=rho2 C 0.000000 0.667450 8.000000 f=rho2 C 0.000000 -0.667450 8.000000 f=rho2 H 0.930241 -1.239503 8.000000 f=rho2 H -0.930241 -1.239503 8.000000 f=rho2 END ALLOW PARTIALSUPERFRAGS FDE PW91K GGAPOTXFD pw91x GGAPOTCFD pw91c END eor rm logfile mv TAPE21 t21.emb.rho1 $ADFBIN/adf << eor Title MODCO: Fragment no. 2; (polarized) EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END CHARGE -1 1 UNRESTRICTED FRAGMENTS rho1 t21.emb.rho1 subfrag=active type=fde rho2 t21.iso.rho2 END ATOMS H 0.930241 1.239503 0.000000 f=rho1 H -0.930241 1.239503 0.000000 f=rho1 C 0.000000 0.667450 0.000000 f=rho1 C 0.000000 -0.667450 0.000000 f=rho1 H 0.930241 -1.239503 0.000000 f=rho1 H -0.930241 -1.239503 0.000000 f=rho1 H 0.930241 1.239503 8.000000 f=rho2 H -0.930241 1.239503 8.000000 f=rho2 C 0.000000 0.667450 8.000000 f=rho2 C 0.000000 -0.667450 8.000000 f=rho2 H 0.930241 -1.239503 8.000000 f=rho2 H -0.930241 -1.239503 8.000000 f=rho2 END ALLOW PARTIALSUPERFRAGS FDE PW91K GGAPOTXFD pw91x GGAPOTCFD pw91c END eor rm logfile mv TAPE21 t21.emb.rho2 it=1 while [ $it -le 2 ]; do $ADFBIN/adf << eor Title MODCO: Fragment no. 1; relaxed EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END NumericalQuality Good CHARGE 1 -1 UNRESTRICTED FRAGMENTS rho1 t21.iso.rho1 rho2 t21.emb.rho2 subfrag=active type=fde END restart file t21.emb.rho1 end ATOMS H 0.930241 1.239503 0.000000 f=rho1 H -0.930241 1.239503 0.000000 f=rho1 C 0.000000 0.667450 0.000000 f=rho1 C 0.000000 -0.667450 0.000000 f=rho1 H 0.930241 -1.239503 0.000000 f=rho1 H -0.930241 -1.239503 0.000000 f=rho1 H 0.930241 1.239503 8.000000 f=rho2 H -0.930241 1.239503 8.000000 f=rho2 C 0.000000 0.667450 8.000000 f=rho2 C 0.000000 -0.667450 8.000000 f=rho2 H 0.930241 -1.239503 8.000000 f=rho2 H -0.930241 -1.239503 8.000000 f=rho2 END ALLOW PARTIALSUPERFRAGS FDE PW91K GGAPOTXFD pw91x GGAPOTCFD pw91c FullGrid Energy END eor rm logfile mv TAPE21 t21.emb.rho1 $ADFBIN/adf << eor Title MODCO: Fragment no. 2; relaxed EPRINT SFO NOEIG NOOVL NOORBPOP END NOPRINT BAS FUNCTIONS SYMMETRY NOSYM XC model SAOP END NumericalQuality Good restart file t21.emb.rho2 end CHARGE -1 1 UNRESTRICTED FRAGMENTS rho1 t21.emb.rho1 subfrag=active type=fde rho2 t21.iso.rho2 END ATOMS H 0.930241 1.239503 0.000000 f=rho1 H -0.930241 1.239503 0.000000 f=rho1 C 0.000000 0.667450 0.000000 f=rho1 C 0.000000 -0.667450 0.000000 f=rho1 H 0.930241 -1.239503 0.000000 f=rho1 H -0.930241 -1.239503 0.000000 f=rho1 H 0.930241 1.239503 8.000000 f=rho2 H -0.930241 1.239503 8.000000 f=rho2 C 0.000000 0.667450 8.000000 f=rho2 C 0.000000 -0.667450 8.000000 f=rho2 H 0.930241 -1.239503 8.000000 f=rho2 H -0.930241 -1.239503 8.000000 f=rho2 END ALLOW PARTIALSUPERFRAGS FDE PW91K GGAPOTXFD pw91x GGAPOTCFD pw91c FullGrid Energy END eor rm logfile mv TAPE21 t21.emb.rho2 it=$(($it+1)) done # ====================================== # NOW THE TAPE21 FILES MUST BE RENAMED # # TO: fragA1.t21, fragA2.t21 # .... up to a max of fragA999.t21 # AND: fragB1.t21, fragB2.t21 # .... up to a max of fragB999.t21 # ====================================== mv t21.emb.rho1 fragB1.t21 mv t21.emb.rho2 fragB2.t21 # ====================================== # Electron Transfer calculation is next # # 1) note the ELECTRONTRANSFER block keyword # 2) hybrids not supported # 3) NumericalQuality GOOD is needed for accuracy # ====================================== $ADFBIN/adf << eor Title ET calculation at R=0.0 Angstrom EPRINT SFO NOEIG NOOVL NOORBPOP SCF NOPOP END NOPRINT BAS FUNCTIONS FRAGMENTS rho1 t21.iso.rho1 rho2 t21.iso.rho2 END ATOMS H 0.930241 1.239503 0.000000 f=rho1 H -0.930241 1.239503 0.000000 f=rho1 C 0.000000 0.667450 0.000000 f=rho1 C 0.000000 -0.667450 0.000000 f=rho1 H 0.930241 -1.239503 0.000000 f=rho1 H -0.930241 -1.239503 0.000000 f=rho1 H 0.930241 1.239503 8.000000 f=rho2 H -0.930241 1.239503 8.000000 f=rho2 C 0.000000 0.667450 8.000000 f=rho2 C 0.000000 -0.667450 8.000000 f=rho2 H 0.930241 -1.239503 8.000000 f=rho2 H -0.930241 -1.239503 8.000000 f=rho2 END NumericalQuality Good UNRESTRICTED CHARGE 0 0 XC GGA PW91 END SYMMETRY nosym SCF iterations 0 END Beckegrid Quality Good END ELECTRONTRANSFER numfrag 2 END eor rm logfile