7.11.10 Examples

Example 7.103  Input for an ADC(2)-s calculation of singlet exited states of methane with D2 symmetry. In total six excited states are requested corresponding to four (two) electronic transitions with irreducible representation $B_{1}$ ($B_{2}$).

$molecule 0 1 C H 1 r0 H 1 r0 2 d0 H 1 r0 2 d0 3 d1 H 1 r0 2 d0 4 d1 r0 = 1.085 d0 = 109.4712206 d1 = 120.0$end

$rem METHOD adc(2) BASIS 6-31g(d,p) MEM_TOTAL 4000 MEM_STATIC 100 EE_SINGLETS [0,4,2,0]$end


Example 7.104  Input for an unrestricted RI-ADC(2)-s calculation with $C_{1}$ symmetry using DIIS. In addition, excited state properties and state-to-state properties are computed.

$molecule 0 2 C 0.0 0.0 -0.630969 N 0.0 0.0 0.540831$end

$rem METHOD adc(2) BASIS aug-cc-pVDZ AUX_BASIS rimp2-aug-cc-pVDZ MEM_TOTAL 4000 MEM_STATIC 100 CC_SYMMETRY false EE_STATES 6 ADC_DO_DIIS true ADC_PROP_ES true ADC_PROP_ES2ES true ADC_PROP_TPA true$end


Example 7.105  Input for a restricted CVS-ADC(2)-x calculation with $C_{1}$ symmetry using 4 parallel CPU cores.

$molecule 0 1 N 1.0706214490 -0.1462996030 0.0000000000 C -0.1838756809 0.3832287690 0.0000000000 O -1.2178351723 -0.2734201303 0.0000000000 H 1.8945772136 0.4351761203 0.0000000000 H 1.1761147729 -1.1515954431 0.0000000000 H -0.1740335498 1.4879608698 0.0000000000$end

$rem METHOD cvs-adc(2)-x EE_SINGLETS 5 ADC_DAVIDSON_MAXSUBSPACE 60 MEM_TOTAL 10000 MEM_STATIC 1000 THREADS 4 CC_SYMMETRY false BASIS 6-31G* ADC_DAVIDSON_THRESH 8 SYMMETRY false ADC_DAVIDSON_MAXITER 900 ADC_CVS true CC_REST_OCC 4$end


Example 7.106  Input for a restricted SF-ADC(2)-s calculation of the first three spin-flip target states of cyclobutadiene without point group symmetry.

$molecule 0 3 C 0.000000 0.000000 0.000000 C 1.439000 0.000000 0.000000 C 1.439000 0.000000 1.439000 C 0.000000 0.000000 1.439000 H -0.758726 0.000000 -0.758726 H 2.197726 0.000000 -0.758726 H 2.197726 0.000000 2.197726 H -0.758726 0.000000 2.197726$end

$rem METHOD adc(2) MEM_TOTAL 15000 MEM_STATIC 1000 CC_SYMMETRY false BASIS 3-21G SF_STATES 3$end


The next example provides input for a restricted ADC(2)-x calculation of water with $C_{s}$ symmetry. Four singlet $A^{\prime\prime}$ excited states and two triplet $A^{\prime}$ excited states are requested. For the first two states (1 ${}^{1}\!A^{\prime\prime}$ and 1 ${}^{3}\!A^{\prime}$) the transition densities as well as the attachment and detachment densities are exported into cube files.

Example 7.107  Restricted ADC(2)-x calculation of water with $C_{s}$ symmetry.

$molecule 0 1 O 0.000 0.000 0.000 H 0.000 0.000 0.950 H 0.896 0.000 -0.317$end

$rem METHOD adc(2)-x BASIS 6-31g(d,p) THREADS 2 MEM_TOTAL 3000 MEM_STATIC 100 EE_SINGLETS [0,4] EE_TRIPLETS [2,0] ADC_PROP_ES true MAKE_CUBE_FILES true$end

$plots Plot transition and a/d densities 40 -3.0 3.0 40 -3.0 3.0 40 -3.0 3.0 0 0 2 2 1 2 1 2$end


The next sample provides input for a ADC(2)-s/ptSS-PCM calculation of the five lowest singlet-excited states of $N,N$-dimethylnitroaniline in diethyl ether. The PCM settings are all default values except THEORY, which is set to IEFPCM instead of the default CPCM.

Example 7.108  DC(2)-s/ptSS-PCM calculation of $N,N$-dimethylnitroaniline in diethyl ether.

$molecule 0 1 C -4.263068 2.512843 0.025391 C -5.030982 1.361365 0.007383 C -4.428196 0.076338 -0.021323 C -3.009941 0.019036 -0.030206 C -2.243560 1.171441 -0.011984 C -2.871710 2.416638 0.015684 H -4.740854 3.480454 0.047090 H -2.502361 -0.932570 -0.052168 H -1.166655 1.104642 -0.020011 H -6.104933 1.461766 0.015870 N -5.178541 -1.053870 -0.039597 C -6.632186 -0.969550 -0.034925 H -6.998203 -0.462970 0.860349 H -7.038179 -1.975370 -0.051945 H -7.001616 -0.431420 -0.910237 C -4.531894 -2.358860 -0.066222 H -3.912683 -2.476270 -0.957890 H -5.298508 -3.126680 -0.075403 H -3.902757 -2.507480 0.813678 N -2.070815 3.621238 0.033076 O -0.842606 3.510489 0.025476 O -2.648404 4.710370 0.054545$end

$rem THREADS 4 METHOD adc(2) BASIS 3-21G MEM_TOTAL 32000 MEM_STATIC 2000 ADC_PROP_ES true ADC_PRINT 1 EE_SINGLETS 5 ADC_DAVIDSON_MAXITER 100 PCM_PRINT 1 !increase print level SOLVENT_METHOD pcm !invokes PCM solvent model$end

$pcm nonequilibrium true theory IEFPCM !default is CPCM, IEFPCM is more accurate Solver Inversion vdwScale 1.20$end

$solvent dielectric 4.34 !epsilon of Et2O dielectric_infi 1.829 !n_square of Et2O$end


The next job requires a rather complicated compound input file. The sample job computes ADC/SS-PCM EqS solvent-field equilibration for the first excited singlet state of peroxinitrite in water, which can be used to compute the fluorescence energy. After generating a starting point in the first job (using a smaller basis and lower ADC convergence criteria), the solvent-field iterations are carried out until convergence in the second job. In the third job, ADC(2) excited states are computed in the converged solvent field that was left on disk by the second Job. In the fourth job, we additionally compute ADC(3) excited states. This mixed approach should in general be used with great caution. If the self-ptSS term of the reference state becomes too large ($>$0.01 eV) like it is the case here, the fully consistent approach should be used, meaning that the solvent reaction field should also be computed at the ADC(3) level. PCM settings are all default values except THEORY, which is set to IEFPCM instead of the default CPCM.

Example 7.109  ADC/SS-PCM EQS solvent-field equilibration for the first excited singlet state of peroxinitrite in water.

$comment ADC(2)/ptSS-PCM to generate starting point for the EqS Step in the next Job$end

$molecule -1 1 N -0.068642000000 -0.600693000000 -0.723424000000 O 0.349666000000 0.711166000000 1.187490000000 O -0.948593000000 0.200668000000 -0.956940000000 O 0.659040000000 -0.386002000000 0.402650000000$end

$rem THREADS 2 METHOD adc(2) BASIS 3-21G !using a small basis to speed up this step MEM_TOTAL 6000 MEM_STATIC 1000 EE_SINGLETS 1 ADC_PROP_ES true ADC_DAVIDSON_CONV 4 SOLVENT_METHOD pcm$end

$pcm nonequilibrium true$end

$solvent !Water dielectric 78.4 dielectric_infi 1.76$end

@@@

$comment ADC(2)/ptSS-PCM(EqS) solvent-field equilibration for the first excited state$end

$molecule read$end

$rem THREADS 2 METHOD adc(2) BASIS 6-31G* MEM_TOTAL 6000 MEM_STATIC 1000 EE_SINGLETS 2 !compute 2 singlets during the equilibration ADC_PROP_ES true SOLVENT_METHOD pcm !activate PCM$end

$pcm eqsolv 15 !maximum 15 steps, converges after 5 eqstate 1 !Equilibrate 1st excited state eqs_conv 4 !Default convergence theory iefpcm nonequilibrium true$end

$solvent dielectric 78.4 dielectric_infi 1.76$end

@@@

$comment Compute ADC(2) excited states in the converged solvent field$end

$molecule read$end

$rem THREADS 2 METHOD adc(2) BASIS 6-31G* MEM_TOTAL 6000 MEM_STATIC 1000 EE_SINGLETS 6 !compute 6 singlets ADC_PROP_ES true ADC_PROP_ES2ES true !compute ES 2 ES transition moments for ESA SOLVENT_METHOD pcm$end

$pcm eqsolv true !only one calculation with converged field eqstate 1 !Equilibrate 1st excited state theory iefpcm nonequilibrium true$end

$solvent dielectric 78.4 dielectric_infi 1.76$end

@@@

$comment We can also compute ADC(3) excited states in the converged ADC(2) solvent field and use the self- ptSS term as diagnostic.$end

$molecule read$end

$rem THREADS 2 METHOD adc(3) BASIS 6-31G* MEM_TOTAL 6000 MEM_STATIC 1000 EE_SINGLETS 3 !compute 3 singlets EE_TRIPLETS 1 !and 1 triplet ADC_PROP_ES true SOLVENT_METHOD pcm$end

$pcm eqsolv true !only one calculation with converged field eqstate 1 !Equilibrate 1st excited state theory iefpcm nonequilibrium true$end

$solvent dielectric 78.4 dielectric_infi 1.76$end


The next sample job provides the input for a RI-ADC(2)/ptSS-PCM(PTED) calculation for the five lowest excited states of peroxinitrite in water. After generating a starting point in the first job, which also provides the ptSS(PTE) and ptSS(PTD) results for comparison, the solvent-field is equilibrated for the MP density in the second job. During the iterations, the calculation of excited states is disabled to speed up the calculation. In the third job, five excited states are computed at the RI-ADC(2)/ptSS(PTED) level of theory. Although the PTD corrections for this molecule are unusually large, a comparison of the PTE, PTD and PTD* results from the first job with the PTED results from the third job will reveal a reasonable agreement between the fully consistent PTED and the perturbative PTD approaches. In the fourth job, excited states are calculated with a larger basis set. The self-ptSS term of the MP ground state will be quite small, showing that the solvent-field computed with the smaller SVP basis is a good approximation.

Example 7.110  RI-ADC(2)/ptSS-PCM(PTED) calculation for the five lowest excited states of peroxinitrite in water.

$comment RI-ADC(2)/ptSS-PCM to generate starting point for the PTED iterations in the next Job and provide PTE and PTD energies for comparing with PTED$end

$molecule -1 1 N -0.068642000000 -0.600693000000 -0.723424000000 O 0.349666000000 0.711166000000 1.187490000000 O -0.948593000000 0.200668000000 -0.956940000000 O 0.659040000000 -0.386002000000 0.402650000000$end

$rem THREADS 2 METHOD adc(2) BASIS def2-SVP AUX_BASIS rimp2-VDZ MEM_TOTAL 6000 MEM_STATIC 1000 EE_SINGLETS 5 ADC_PROP_ES true SOLVENT_METHOD pcm$end

$pcm nonequilibrium true$end

$solvent !Water dielectric 78.4 dielectric_infi 1.76$end

@@@

$comment RI-ADC(2)/ptSS-PTED solvent-field equilibration for the MP ground state. No excited states are computed$end

$molecule read$end

$rem THREADS 2 METHOD adc(2) BASIS def2-SVP AUX_BASIS rimp2-VDZ MEM_TOTAL 6000 MEM_STATIC 1000 EE_SINGLETS 0 !dont compute ES ADC_PROP_ES true SOLVENT_METHOD pcm !activate PCM$end

$pcm eqsolv 15 !maximum 15 steps eqstate 0 !Equilibrate MP ground state eqs_conv 5 !higher convergence theory iefpcm nonequilibrium true$end

$solvent dielectric 78.4 dielectric_infi 1.76$end

@@@

$comment Compute ADC(2)/ptSS-PTED excited states in the converged solvent field$end

$molecule read$end

$rem THREADS 2 METHOD adc(2) BASIS def2-SVP AUX_BASIS rimp2-VDZ MEM_TOTAL 6000 MEM_STATIC 1000 EE_SINGLETS 5 !compute 5 singlets ADC_PROP_ES true SOLVENT_METHOD pcm$end

$pcm eqsolv true !only one calculation with converged field eqstate 0 !Equilibrate MP ground state theory iefpcm nonequilibrium true$end

$solvent dielectric 78.4 dielectric_infi 1.76$end

@@@

$comment We can also compute the ES in the converged field with a larger basis and without RI in the stored solvent-field.$end

$molecule read$end

$rem THREADS 2 METHOD adc(2) BASIS def2-TZVP MEM_TOTAL 6000 MEM_STATIC 1000 EE_SINGLETS 3 !compute 3 singlets ADC_PROP_ES true SOLVENT_METHOD pcm$end

$pcm eqsolv true !only one calculation with converged field eqstate 0 !Equilibrate MP ground state theory iefpcm nonequilibrium true$end

$solvent dielectric 78.4 dielectric_infi 1.76$end