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=== Analytic derivative approach === === Finite-difference approach === {{{ |
The calculations of first-order nonadiabatic couplings (NAC) between ground and excited-states ('''<0|Dx|Sn>'''), and those between the excited-states ('''<Sm|Dx|Sn>''' or '''<Tm|Dx|Tn>''') at the TD-DFT/TDA level can be achieved by generalizing the standard linear and quadratic response theories, for details, see ''Zhendong Li and Wenjian Liu, "First-order nonadiabatic coupling matrix elements between excited states: A Lagrangian formulation at the CIS, RPA, TD-HF, and TD-DFT levels", J. Chem. Phys. 141, 014110 (2014). '' For convenience, however, in the input they are both specified by the '''QUAD''' keyword with '''single''' and '''double''', respectively. Either analytic derivative or finite difference approach can be used. The latter is only allowed for C(1) symmetry, and for molecules without orbital degeneracy! == Compared with Hellman-Feynman results == '''By using the turn over rule, the NAC between two adiabatic states can be written as a integration of the gradients of V_nuc and the transition density scaled by the energy difference.''' We may call it Hellman-Feynman like expression. However, for real application, either the state is exact nor the basis is complete, so this form will not yield accurate results !!! As an illustration we consider the NAC between two triplet states of MgH2 calculated at the pp-TDA level using several different basis sets. pp-tda for MgH2: {{{ |
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| sto-3g | aug-cc-pvqz uncontracted # nac-mg #primitives |
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| C 0.00000000 -1.20809142 -1.14173975 C 0.00000000 -1.20797607 0.25342015 C 0.00000000 0.00000000 0.95085852 C -0.00000000 1.20797607 0.25342015 C -0.00000000 1.20809142 -1.14173975 C 0.00000000 0.00000000 -1.83922155 H 0.00000000 -2.16045397 -1.69142002 H 0.00000000 -2.16044427 0.80300713 H -0.00000000 2.16044427 0.80300713 H -0.00000000 2.16045397 -1.69142002 H 0.00000000 0.00000000 -2.93882555 F 0.00000000 0.00000000 2.30085848 |
Mg 0. 0. 5.0 H 0. 1.25 0. H 0. -1.25 0. End geometry units bohr skeleton $END $xuanyuan direct schwarz $end $scf RHF charge 2 spin 1 THRESHCONV 1.d-12 1.d-10 OPTSCR 1 $end $tddft imethod 4 isf 1 nexit 0 0 2 0 itda 1 ipprpa 1 idiag 1 istore 1 crit_e 1.d-12 crit_vec 1.d-10 $end $resp iprt 2 QUAD FNAC norder 1 method 2 nfiles 1 $end }}} refbas (s/p): {{{ No. Pair ExSym ExEnergies f D<S^2> Dominant Excitations IPA Ova En-E1 1 B1 1 B1 -18.6728 eV 0.0000 0.0000 92.8% VV(1): B1( 2 )-> A1( 5 ) -23.956 0.000 0.0000 2 B1 2 B1 -16.3909 eV 0.0000 0.0000 88.4% VV(1): B1( 3 )-> A1( 5 ) -21.065 0.000 2.2819 ... Gradient contribution from Final-NAC(R)-HFey 1 -0.0000000000 -0.0000000000 -0.7243310867 2 0.3451224889 0.0000000000 0.0561331731 3 -0.3451224889 -0.0000000000 0.0561331731 Sum of gradient contribution from Final-NAC(R)-HFey -0.0000000000 -0.0000000000 -0.6120647404 ... Gradient contribution from Final-NAC(R)-Escaled 1 -0.0000000000 -0.0000000000 0.3549353015 2 0.7989929157 0.0000000000 -0.1473168767 3 -0.7989929157 -0.0000000000 -0.1473168774 Sum of gradient contribution from Final-NAC(R)-Escaled -0.0000000000 -0.0000000000 0.0603015474 }}} aug-cc-pVTZ: {{{ No. Pair ExSym ExEnergies f D<S^2> Dominant Excitations IPA Ova En-E1 1 B1 1 B1 -18.6736 eV 0.0000 0.0000 90.6% VV(1): B1( 2 )-> A1( 5 ) -23.766 0.000 0.0000 2 B1 2 B1 -16.9243 eV 0.0000 0.0000 87.8% VV(1): B1( 3 )-> A1( 5 ) -21.638 0.000 1.7493 ... Gradient contribution from Final-NAC(R)-HFey 1 -0.0000000000 -0.0000000000 -0.2135694894 2 0.3992751267 -0.0000000000 0.0624241280 3 -0.3992751267 -0.0000000000 0.0624241280 Sum of gradient contribution from Final-NAC(R)-HFey -0.0000000000 -0.0000000000 -0.0887212334 ... Gradient contribution from Final-NAC(R)-Escaled 1 0.0000000000 -0.0000000000 0.3849500968 2 0.8010940332 0.0000000000 -0.1247569146 3 -0.8010940332 -0.0000000000 -0.1247570212 Sum of gradient contribution from Final-NAC(R)-Escaled 0.0000000000 -0.0000000000 0.1354361609 }}} == Analytic derivative approach == NAC between two ^1^A2 states of CH2O: {{{ $COMPASS Title ch2o Basis 6-31GP Geometry C 0.00000000 -0.00000000 -0.53964037 O 0.00000000 0.00000000 0.68767663 H 0.00000000 0.93940400 -1.13178537 H 0.00000000 -0.93940400 -1.13178537 End geometry skeleton $END $xuanyuan direct schwarz $end $scf RHF charge 0 spin 1 THRESHCONV 1.d-10 1.d-8 OPTSCR 1 $end $tddft imethod 1 isf 0 nexit 0 2 0 0 itda 0 idiag 1 istore 1 crit_e 1.d-10 crit_vec 1.d-8 lefteig DirectGrid $end $resp iprt 1 QUAD FNAC double pairs 1 1 2 1 1 2 2 norder 1 method 2 nfiles 1 ignore 1 noresp $end }}} == Finite difference approach == To use the finite difference approach, '''nosym''' must be used to avoid the rotation of molecules. Currently, only C(1) group is permitted. For the example considered above, it turns out that the first two ^1^A2 excited states are the 1st and 4th excited states. However, if only use '''iexit=4''' with iterative diagonalization, the initialization based on orbital energy difference (IPA) will miss the 2rd excited states, as its IPA is very large, viz., {{{ No. Pair ExSym ExEnergies f D<S^2> Dominant Excitations IPA Ova En-E1 1 A 2 A 4.3504 eV 0.0000 0.0000 88.9% CV(0): A( 8 )-> A( 9 ) 15.558 0.476 0.0000 2 A 3 A 9.3394 eV 0.0008 0.0000 92.4% CV(0): A( 6 )-> A( 9 ) 21.045 0.546 4.9890 3 A 4 A 9.3480 eV 0.1782 0.0000 85.8% CV(0): A( 7 )-> A( 9 ) 17.814 0.822 4.9975 4 A 5 A 11.3372 eV 0.0000 0.0000 92.3% CV(0): A( 5 )-> A( 9 ) 22.197 0.535 6.9868 5 A 6 A 11.6654 eV 0.3266 0.0000 92.9% CV(0): A( 8 )-> A( 10 ) 18.527 0.461 7.3150 }}} Thus, '''iexit=5''' is used in the following inputs: {{{ $COMPASS Title ch2o Basis 6-31GP Geometry C 0.00000000 -0.00000000 -0.53964037 O 0.00000000 0.00000000 0.68767663 H 0.00000000 0.93940400 -1.13178537 H 0.00000000 -0.93940400 -1.13178537 |
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| iaufbau 0 |
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| 2 | 5 |
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| 1 | 0 idiag 1 istore 1 crit_e 1.d-10 crit_vec 1.d-8 lefteig DirectGrid $end $resp iprt 1 QUAD FNAC double pairs 1 1 1 1 1 1 4 norder 1 method 2 nfiles 1 ignore 1 noresp $end }}} The corresponding input for the finite difference approach is to add two keywords: '''FDIF''' for specification and '''step''' followed by a real number for step size in finite difference. If the unit is bohr in the COMPASS part, the 'BOHR' should be added in the RESP part also. {{{ $COMPASS Title ch2o Basis 6-31GP Geometry C 0.00000000 -0.00000000 -0.53964037 O 0.00000000 0.00000000 0.68767663 H 0.00000000 0.93940400 -1.13178537 H 0.00000000 -0.93940400 -1.13178537 End geometry skeleton group c(1) nosym $END $xuanyuan direct schwarz $end $scf RHF charge 0 spin 1 THRESHCONV 1.d-10 1.d-8 OPTSCR 1 iaufbau 0 $end $tddft imethod 1 isf 0 iexit 5 itda 0 |
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| single states 1 1 1 2 |
#single #states #1 #1 1 2 |
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| 1 1 1 1 1 2 | 1 1 1 1 1 4 |
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| To use finite-difference, a script '''fdiff.py''' should be used as {{{ ./fbdiff.py run.sh input.inp > log }}} After the calculation is done, an output file '''input.out''' will present in the current directory. The '''log''' file saves the information during the calculations. Note: If '''FDIF''' is omitted, the analytic calculation will be carried out by simply using the '''run.sh''' script. |
To use finite-difference, a script '''fdiff.py''' along with '''fdmol.py''' in '''bdf-pkg/source/tools/fdiff''' should be used as {{{ ./fbdiff.py run.sh xxx.inp > log }}} After the calculation is done, an output file '''xxx.out''' will present in the current directory. The '''log''' file saves the information during the calculations. == Illustration == Visualisation of the results can be achieved via the tools in '''bdf-pkg/source/tools/fdiff/NACplot.nb'''. Static: [[attachment:t1_nac.PNG]] Dynamic: [[attachment:t1_nac.GIF]] |
First-order nonadiabatic couplings
The calculations of first-order nonadiabatic couplings (NAC) between ground and excited-states (<0|Dx|Sn>), and those between the excited-states (<Sm|Dx|Sn> or <Tm|Dx|Tn>) at the TD-DFT/TDA level can be achieved by generalizing the standard linear and quadratic response theories, for details, see
Zhendong Li and Wenjian Liu, "First-order nonadiabatic coupling matrix elements between excited states: A Lagrangian formulation at the CIS, RPA, TD-HF, and TD-DFT levels", J. Chem. Phys. 141, 014110 (2014).
For convenience, however, in the input they are both specified by the QUAD keyword with single and double, respectively. Either analytic derivative or finite difference approach can be used. The latter is only allowed for C(1) symmetry, and for molecules without orbital degeneracy!
Compared with Hellman-Feynman results
By using the turn over rule, the NAC between two adiabatic states can be written as a integration of the gradients of V_nuc and the transition density scaled by the energy difference. We may call it Hellman-Feynman like expression.
However, for real application, either the state is exact nor the basis is complete, so this form will not yield accurate results !!! As an illustration we consider the NAC between two triplet states of MgH2 calculated at the pp-TDA level using several different basis sets.
pp-tda for MgH2:
$COMPASS Title nh3 Basis aug-cc-pvqz uncontracted # nac-mg #primitives Geometry Mg 0. 0. 5.0 H 0. 1.25 0. H 0. -1.25 0. End geometry units bohr skeleton $END $xuanyuan direct schwarz $end $scf RHF charge 2 spin 1 THRESHCONV 1.d-12 1.d-10 OPTSCR 1 $end $tddft imethod 4 isf 1 nexit 0 0 2 0 itda 1 ipprpa 1 idiag 1 istore 1 crit_e 1.d-12 crit_vec 1.d-10 $end $resp iprt 2 QUAD FNAC norder 1 method 2 nfiles 1 $end
refbas (s/p):
No. Pair ExSym ExEnergies f D<S^2> Dominant Excitations IPA Ova En-E1
1 B1 1 B1 -18.6728 eV 0.0000 0.0000 92.8% VV(1): B1( 2 )-> A1( 5 ) -23.956 0.000 0.0000
2 B1 2 B1 -16.3909 eV 0.0000 0.0000 88.4% VV(1): B1( 3 )-> A1( 5 ) -21.065 0.000 2.2819
...
Gradient contribution from Final-NAC(R)-HFey
1 -0.0000000000 -0.0000000000 -0.7243310867
2 0.3451224889 0.0000000000 0.0561331731
3 -0.3451224889 -0.0000000000 0.0561331731
Sum of gradient contribution from Final-NAC(R)-HFey
-0.0000000000 -0.0000000000 -0.6120647404
...
Gradient contribution from Final-NAC(R)-Escaled
1 -0.0000000000 -0.0000000000 0.3549353015
2 0.7989929157 0.0000000000 -0.1473168767
3 -0.7989929157 -0.0000000000 -0.1473168774
Sum of gradient contribution from Final-NAC(R)-Escaled
-0.0000000000 -0.0000000000 0.0603015474aug-cc-pVTZ:
No. Pair ExSym ExEnergies f D<S^2> Dominant Excitations IPA Ova En-E1
1 B1 1 B1 -18.6736 eV 0.0000 0.0000 90.6% VV(1): B1( 2 )-> A1( 5 ) -23.766 0.000 0.0000
2 B1 2 B1 -16.9243 eV 0.0000 0.0000 87.8% VV(1): B1( 3 )-> A1( 5 ) -21.638 0.000 1.7493
...
Gradient contribution from Final-NAC(R)-HFey
1 -0.0000000000 -0.0000000000 -0.2135694894
2 0.3992751267 -0.0000000000 0.0624241280
3 -0.3992751267 -0.0000000000 0.0624241280
Sum of gradient contribution from Final-NAC(R)-HFey
-0.0000000000 -0.0000000000 -0.0887212334
...
Gradient contribution from Final-NAC(R)-Escaled
1 0.0000000000 -0.0000000000 0.3849500968
2 0.8010940332 0.0000000000 -0.1247569146
3 -0.8010940332 -0.0000000000 -0.1247570212
Sum of gradient contribution from Final-NAC(R)-Escaled
0.0000000000 -0.0000000000 0.1354361609
Analytic derivative approach
NAC between two 1A2 states of CH2O:
$COMPASS Title ch2o Basis 6-31GP Geometry C 0.00000000 -0.00000000 -0.53964037 O 0.00000000 0.00000000 0.68767663 H 0.00000000 0.93940400 -1.13178537 H 0.00000000 -0.93940400 -1.13178537 End geometry skeleton $END $xuanyuan direct schwarz $end $scf RHF charge 0 spin 1 THRESHCONV 1.d-10 1.d-8 OPTSCR 1 $end $tddft imethod 1 isf 0 nexit 0 2 0 0 itda 0 idiag 1 istore 1 crit_e 1.d-10 crit_vec 1.d-8 lefteig DirectGrid $end $resp iprt 1 QUAD FNAC double pairs 1 1 2 1 1 2 2 norder 1 method 2 nfiles 1 ignore 1 noresp $end
Finite difference approach
To use the finite difference approach, nosym must be used to avoid the rotation of molecules. Currently, only C(1) group is permitted. For the example considered above, it turns out that the first two 1A2 excited states are the 1st and 4th excited states. However, if only use iexit=4 with iterative diagonalization, the initialization based on orbital energy difference (IPA) will miss the 2rd excited states, as its IPA is very large, viz.,
No. Pair ExSym ExEnergies f D<S^2> Dominant Excitations IPA Ova En-E1
1 A 2 A 4.3504 eV 0.0000 0.0000 88.9% CV(0): A( 8 )-> A( 9 ) 15.558 0.476 0.0000
2 A 3 A 9.3394 eV 0.0008 0.0000 92.4% CV(0): A( 6 )-> A( 9 ) 21.045 0.546 4.9890
3 A 4 A 9.3480 eV 0.1782 0.0000 85.8% CV(0): A( 7 )-> A( 9 ) 17.814 0.822 4.9975
4 A 5 A 11.3372 eV 0.0000 0.0000 92.3% CV(0): A( 5 )-> A( 9 ) 22.197 0.535 6.9868
5 A 6 A 11.6654 eV 0.3266 0.0000 92.9% CV(0): A( 8 )-> A( 10 ) 18.527 0.461 7.3150Thus, iexit=5 is used in the following inputs:
$COMPASS Title ch2o Basis 6-31GP Geometry C 0.00000000 -0.00000000 -0.53964037 O 0.00000000 0.00000000 0.68767663 H 0.00000000 0.93940400 -1.13178537 H 0.00000000 -0.93940400 -1.13178537 End geometry skeleton group c(1) nosym $END $xuanyuan direct schwarz $end $scf RHF charge 0 spin 1 THRESHCONV 1.d-10 1.d-8 OPTSCR 1 $end $tddft imethod 1 isf 0 iexit 5 itda 0 idiag 1 istore 1 crit_e 1.d-10 crit_vec 1.d-8 lefteig DirectGrid $end $resp iprt 1 QUAD FNAC double pairs 1 1 1 1 1 1 4 norder 1 method 2 nfiles 1 ignore 1 noresp $end
The corresponding input for the finite difference approach is to add two keywords: FDIF for specification and step followed by a real number for step size in finite difference. If the unit is bohr in the COMPASS part, the 'BOHR' should be added in the RESP part also.
$COMPASS Title ch2o Basis 6-31GP Geometry C 0.00000000 -0.00000000 -0.53964037 O 0.00000000 0.00000000 0.68767663 H 0.00000000 0.93940400 -1.13178537 H 0.00000000 -0.93940400 -1.13178537 End geometry skeleton group c(1) nosym $END $xuanyuan direct schwarz $end $scf RHF charge 0 spin 1 THRESHCONV 1.d-10 1.d-8 OPTSCR 1 iaufbau 0 $end $tddft imethod 1 isf 0 iexit 5 itda 0 idiag 1 istore 1 crit_e 1.d-10 crit_vec 1.d-8 lefteig AOKXC DirectGrid $end $resp iprt 1 QUAD FNAC #single #states #1 #1 1 2 double pairs 1 1 1 1 1 1 4 norder 1 method 2 nfiles 1 FDIF step 0.001 ignore 1 noresp $end
To use finite-difference, a script fdiff.py along with fdmol.py in bdf-pkg/source/tools/fdiff should be used as
./fbdiff.py run.sh xxx.inp > log
After the calculation is done, an output file xxx.out will present in the current directory. The log file saves the information during the calculations.
Illustration
Visualisation of the results can be achieved via the tools in bdf-pkg/source/tools/fdiff/NACplot.nb.
Static: t1_nac.PNG
Dynamic: t1_nac.GIF
