.. tip:: All input files can be downloaded: :download:`Files `. .. tip:: For more information of this section, please refer to these keywords: - :doc:`../keywords/eda` - :doc:`tso1` - :doc:`tso2` Multi-State Energy Decomposition Analysis for Exciplexes ============================================================== .. contents:: :local: This tutorial will lead you step by step to do multi-state energy decomposition analysis (MS-EDA) for exciplexes using Qbics. .. hint:: If you use Qbics to do MS-EDA in you paper, please cite the following references: - `JACS Au 2023, 3, 1800-1819. `_ - `J. Phys. Chem. Lett. 2023, 14, 2917-2926. `_ Theory: How to Decompose the Exciplex Energy --------------------------------------------------------- Input ------------------------- Below, we consider 3 exciplexes: (MeOCH=CH\ :sub:`2`\ )(TCNE), acetone dimer, and (C\ :sub:`6`\ H\ :sub:`6`\ )-(cis-2-butadiene). .. figure:: figs/a57.png Their input files are shown below: .. tabs:: .. tab:: (MeOCH=CH\ :sub:`2`\ )(TCNE) .. code-block:: :caption: tn.inp :linenos: :emphasize-lines: 39-41, 43-45,47-48 mol C -0.198382 0.676975 0.839378 C -1.315863 0.038931 0.405996 C -2.225365 0.670286 -0.508436 N -2.959552 1.174482 -1.247154 C -1.634267 -1.289698 0.850726 N -1.901673 -2.352749 1.221105 C 0.723624 0.024005 1.725081 N 1.483401 -0.507944 2.417545 C 0.131547 2.005023 0.406927 N 0.406859 3.079229 0.077027 C -0.018608 -1.360064 -2.097094 C 1.086004 -1.277514 -1.352322 H -0.458263 -2.333443 -2.305731 H -0.471114 -0.462748 -2.522620 H 1.590935 -2.157076 -0.934177 O 1.621801 -0.078506 -1.011442 C 2.981195 -0.123945 -0.597217 H 3.629890 -0.409943 -1.438672 H 3.239414 0.887438 -0.263120 H 3.112168 -0.831294 0.237956 end basis cc-pvdz end scf charge 0 spin2p1 1 type u end eda type mseda frag 0 1 1-10 frag 0 1 11-20 # Orbital partition for fragment 1 orb1 64 1 1-31 33-140 : 1-139 orb1 0 1 32 : 140 orb1 32 1 141-226 : 141-226 # Orbital partition for fragment 2 orb2 64 1 1-140 : 1-140 orb2 32 1 141-155 157-226 : 141-225 orb2 0 1 156 : 226 # Orbital partition for the whole molecule orb 96 1 1-47 49-226 : 1-225 orb 0 1 48 : 226 end task eda m062x end .. tab:: acetone dimer .. code-block:: :caption: a2.inp :linenos: mol C 1.40501800 0.00020500 0.16613500 O 1.96732200 0.00002100 1.32250100 C 1.50655000 -1.29318400 -0.61925100 H 2.50836500 -1.41216900 -1.04690200 H 1.29901100 -2.14677000 0.02291600 H 0.76955900 -1.24977400 -1.42041200 C 1.50473300 1.29462300 -0.61784400 H 2.50613100 1.41506600 -1.04604700 H 0.76730100 1.25123500 -1.41860400 H 1.29676400 2.14733100 0.02537900 C -1.57069600 -0.00057700 -0.15915200 O -1.45955200 -0.00147400 -1.36266600 C -1.67202400 1.28071400 0.63059600 H -0.94198800 1.27894000 1.44059400 H -1.51130700 2.13358300 -0.02305300 H -2.66412500 1.34977500 1.08181900 C -1.67029600 -1.28074500 0.63266100 H -1.50557100 -2.13424000 -0.01918900 H -0.94255800 -1.27573200 1.44471600 H -2.66346000 -1.35183900 1.08123100 end basis cc-pvdz end scf charge 0 spin2p1 1 type u end eda type mseda frag 0 1 1-10 frag 0 1 11-20 # Orbital partition for fragment 1 orb1 32 1 1-15 17-86 : 1-85 orb1 0 1 16 : 86 orb1 32 1 87-172 : 87-172 # Orbital partition for fragment 2 orb2 32 1 1-86 : 1-86 orb2 32 1 87-101 103-172 : 87-171 orb2 0 1 102 : 172 # Orbital partition for the whole molecule orb 64 1 1-31 33-172 : 1-171 orb 0 1 32 : 172 end task eda m062x end .. tab:: (C\ :sub:`6`\ H\ :sub:`6`\ )-(cis-2-butadiene) .. code-block:: :caption: da.inp :linenos: mol C -2.11437643657060 -0.85754420403449 0.63184430021191 C -1.32991002940312 -1.39329844967993 1.63831931176558 C -1.81293019105347 1.33073311710706 1.56276237609516 C -2.35633843770169 0.50460524003657 0.59424676783581 H -2.53847350527233 -1.50253884729794 -0.12405889027395 H -1.14410843273496 -2.45741464148384 1.66881048558538 H -2.00660926253103 2.39379539743948 1.53656866553163 H -2.97003559294189 0.92298308733968 -0.19048089761824 C -1.02440574134394 0.79568848439314 2.56656836295313 H -0.59784058966710 1.44121012207980 3.32083332927968 C -0.78405589408731 -0.56662507682690 2.60499448062254 H -0.17129827655707 -0.98413854716428 3.39102605834755 C 0.90530915148513 0.76859614859683 -0.69280985547464 H 0.20967383636766 0.86860902650722 -1.51685088520083 C 1.30597277062083 -0.44559901705687 -0.35097796744746 H 0.92486814437303 -1.29036878583159 -0.91133975839400 C 2.25957249832950 -0.81731353879967 0.73692864900559 H 1.83711847972095 -1.62131069441208 1.33810967176003 H 3.19277121604849 -1.18163197052739 0.30437410302004 H 2.48581415297725 0.02130187194289 1.38838793614305 C 1.30766703567951 2.06806699673986 -0.07669642598883 H 1.87877136546791 2.65714541611658 -0.79526222872770 H 0.41956249793524 2.63960219031429 0.18894978225370 H 1.91208124086554 1.93108667450115 0.81435262871432 end basis cc-pvdz end scf charge 0 spin2p1 1 type u end eda type mseda frag 0 1 1-12 frag 0 1 13-24 # Orbital partition for fragment 1 orb1 42 1 1-20 22-114 : 1-113 orb1 0 1 21 : 114 orb1 32 1 115-210 : 115-210 # Orbital partition for fragment 2 orb2 42 1 1-114 : 1-114 orb2 32 1 115-129 131-210 : 115-209 orb2 0 1 130 : 210 # Orbital partition for the whole molecule orb 74 1 1-36 38-210 : 1-209 orb 0 1 37 : 210 end task eda m062x end We will take one example to explain the input, i.e., (MeOCH=CH\ :sub:`2`\ )(TCNE). Before proceeding, you should have read :doc:`tso1` to understand how to use TSO-DFT to get the excited states. For the exciplex, we will use ``type mseda`` to do MS-EDA, and the fragments should be given by ``frag`` option. This is the same as the ``eda`` keyword in :doc:`../keywords/eda`. Now, we will use ``orb`` option to set the excited state of the whole exciplex. See Line 47-48. This is a 48 → 49 (HOMO → LUMO) singlet excited state. We partition the oribtals into 2 subspaces. By putting alpha 48 and beta 226 into a subspace with zero electrons, the Aufbau occupation of the first subspace naturally leads to the HOMO-LUMO transition. Of course, you can consider other excitations. .. figure:: figs/a58.png Then, we will use ``orb1`` and ``orb2`` options to set the diabatic excited states (MeOCH=CH\ :sub:`2`\ \*)(TCNE) and (MeOCH=CH\ :sub:`2`\ )(TCNE\*). See Line 39-41 and 43-45. Below, in the left panel, we show the diabatic state of (MeOCH=CH\ :sub:`2`\ \*)(TCNE), where the wave functions are localized on its own fragment. This state is assigned by ``frag`` automatically. In the right panel, we show the diabatic excited state of (MeOCH=CH\ :sub:`2`\ \*)(TCNE). We partition the orbitals into 3 subspaces. By putting alpha 32 and beta 140 into a subspace with zero electrons, the Aufbau occupation of the first subspace naturally leads to the HOMO-LUMO transition of MeOCH=CH\ :sub:`2`\ . For the third subspace, we keep it unchanged as in the diabatic state, so TCNE is in the ground state. .. figure:: figs/a59.png By the same logic, we can set the diabatic excited state of (MeOCH=CH\ :sub:`2`\ )(TCNE\*) using ``orb2`` option. See Line 43-45. .. figure:: figs/a60.png Finally, we can calculate the exciplex energy using ``eda m062x`` in the ``task`` section. Here, we want to study the relationship between the HOMO-LUMO transition of the exciplex and the HOMO-LUM transition of the fragments. You can set ``orb1`` and ``orb2`` options to use other excited states. For the other two exciplexes, the input files are written in the same way. Output ------------------------- After running the calculation, we will get the following output files. We again take (MeOCH=CH\ :sub:`2`\ )(TCNE) as an example. .. tabs:: .. tab:: (MeOCH=CH\ :sub:`2`\ )(TCNE) .. code-block:: :caption: tn.out :linenos: :emphasize-lines: 7,14, 22,33, 47,53, 57-64, 66-69 ---- NOSI Results ---- ====================== State NOSI Energies Excited Energy Osc. Str. DX DY DZ (Hartree) (eV) (a.u.) (a.u.) (a.u.) 0 -640.36742765 0.00000000 0.00000000 -0.96550 0.43709 0.00378 1 -640.32444246 1.16962698 0.00000331 -0.01186 -0.00940 -0.00159 2 -640.25510627 3.05626471 0.00000000 0.00000 0.00000 0.00000 3 -640.15547535 5.76722204 0.00000000 0.00000 0.00000 0.00000 ---- NOSI State Identification (Coefficients) ---- ================================================== State |0> = +0.707 |tn-Ax.B.mwfn> -0.707 |spin_flip_tn-Ax.B.mwfn> State |1> = -0.707 |tn-A.Bx.mwfn> +0.707 |spin_flip_tn-A.Bx.mwfn> State |2> = -0.698 |tn-Ax.B.mwfn> -0.698 |spin_flip_tn-Ax.B.mwfn> +0.111 |tn-A.Bx.mwfn> +0.111 |spin_flip_tn-A.Bx. mwfn> State |3> = +0.111 |tn-Ax.B.mwfn> +0.111 |spin_flip_tn-Ax.B.mwfn> +0.698 |tn-A.Bx.mwfn> +0.698 |spin_flip_tn-A.Bx. mwfn> --omitted-- ---- NOSI Results ---- ====================== State NOSI Energies Excited Energy Osc. Str. DX DY DZ (Hartree) (eV) (a.u.) (a.u.) (a.u.) 0 -640.36749379 0.00000000 0.00000000 -0.98365 0.43935 0.01448 1 -640.34091881 0.72310508 0.00000000 0.00000 -0.00000 -0.00000 2 -640.33660378 0.84051710 0.00145069 0.28743 -0.09118 -0.22446 3 -640.32372617 1.19091695 0.00009900 0.05373 -0.03170 -0.05398 4 -640.25509855 3.05827441 0.00000000 0.00000 0.00000 0.00000 5 -640.15527583 5.77445072 0.00000000 0.00000 0.00000 0.00000 6 -640.07534938 7.94924924 0.00077286 -0.02996 0.05389 0.06448 7 -640.07504770 7.95745814 0.00000000 0.00000 -0.00000 -0.00000 ---- NOSI State Identification (Coefficients) ---- ================================================== State |0> = -0.706 |tn-Ax.B.mwfn> +0.706 |spin_flip_tn-Ax.B.mwfn> State |1> = +0.705 |tn-A-.B+.mwfn> +0.705 |spin_flip_tn-A-.B+.mwfn> State |2> = -0.152 |tn-A.Bx.mwfn> +0.152 |spin_flip_tn-A.Bx.mwfn> -0.688 |tn-A-.B+.mwfn> +0.688 |spin_flip_tn-A-.B +.mwfn> State |3> = +0.691 |tn-A.Bx.mwfn> -0.691 |spin_flip_tn-A.Bx.mwfn> -0.168 |tn-A-.B+.mwfn> +0.168 |spin_flip_tn-A-.B +.mwfn> State |4> = +0.698 |tn-Ax.B.mwfn> +0.698 |spin_flip_tn-Ax.B.mwfn> -0.111 |tn-A.Bx.mwfn> -0.111 |spin_flip_tn-A.Bx. mwfn> State |5> = +0.111 |tn-Ax.B.mwfn> +0.111 |spin_flip_tn-Ax.B.mwfn> +0.699 |tn-A.Bx.mwfn> +0.699 |spin_flip_tn-A.Bx. mwfn> State |6> = +0.707 |tn-A+.B-.mwfn> -0.707 |spin_flip_tn-A+.B-.mwfn> State |7> = +0.707 |tn-A+.B-.mwfn> +0.707 |spin_flip_tn-A+.B-.mwfn> --omitted-- ---- NOSI Results ---- ====================== State NOSI Energies Excited Energy Osc. Str. DX DY DZ (Hartree) (eV) (a.u.) (a.u.) (a.u.) 0 -640.46151149 0.00000000 0.00000000 -1.39398 0.68556 0.39128 1 -640.34568876 3.15153658 0.00000000 0.00019 0.00008 -0.00003 2 -640.33525702 3.43538409 0.16461516 -1.15897 0.76059 1.41473 ---- NOSI State Identification (Coefficients) ---- ================================================== State |0> = -1.000 |tn-AB.mwfn> State |1> = -0.711 |tn-ABx.mwfn> +0.711 |spin_flip_tn-ABx.mwfn> State |2> = +0.703 |tn-ABx.mwfn> +0.703 |spin_flip_tn-ABx.mwfn> --omitted-- MS-EDA Results ============== E[A]+E[B] = -640.44244734 Hartree -> 0.00000 eV (as reference) E[A.B] = -640.45105170 Hartree -> -0.23414 eV E[A+.B-] = -640.07545516 Hartree -> 9.98637 eV E[A-.B+] = -640.33851873 Hartree -> 2.82804 eV E[Ax.B] = -640.31003238 Hartree -> 3.60319 eV E[A.Bx] = -640.24118378 Hartree -> 5.47666 eV E[AB] = -640.46138548 Hartree -> -0.51533 eV E[ABx] = -640.34047390 Hartree -> 2.77484 eV delta E_Lint = E[A.B]-(E[A]+E[B]) = -0.00860437 Hartree = -0.23414 eV delta E_exciton = E[exciton]-E[A.B] delta delta E_superexchange = E[SE]-E[exciton] delta delta E_OCD = E[es]-E[SE] For E[es], E[SE], and E[exciton], you will have to manually select from "NOSI Results" according to "NOSI State Identification (Coefficients)". .. tab:: acetone dimer .. code-block:: :caption: a2.inp :linenos: ---- NOSI Results ---- ====================== State NOSI Energies Excited Energy Osc. Str. DX DY DZ (Hartree) (eV) (a.u.) (a.u.) (a.u.) 0 -386.02163213 0.00000000 0.00000000 0.39326 -0.00146 -0.23314 1 -386.00338586 0.49648108 0.00000000 -0.00000 0.00000 -0.00000 2 -385.97347538 1.31034511 0.00000035 0.00154 0.00000 0.00445 3 -385.95321735 1.86156604 0.00000000 -0.00000 -0.00000 -0.00000 ---- NOSI State Identification (Coefficients) ---- ================================================== State |0> = -0.707 |a2-Ax.B.mwfn> +0.707 |spin_flip_a2-Ax.B.mwfn> State |1> = +0.707 |a2-Ax.B.mwfn> +0.707 |spin_flip_a2-Ax.B.mwfn> State |2> = -0.707 |a2-A.Bx.mwfn> +0.707 |spin_flip_a2-A.Bx.mwfn> State |3> = -0.707 |a2-A.Bx.mwfn> -0.707 |spin_flip_a2-A.Bx.mwfn> --omitted-- ---- NOSI Results ---- ====================== State NOSI Energies Excited Energy Osc. Str. DX DY DZ (Hartree) (eV) (a.u.) (a.u.) (a.u.) 0 -386.02358380 0.00000000 0.00000000 0.27272 -0.00152 -0.23905 1 -386.00574867 0.48529396 0.00000000 0.00000 -0.00000 0.00000 2 -385.97730787 1.25916817 0.00001237 0.02577 0.00001 0.01185 3 -385.95818745 1.77943483 0.00000000 -0.00000 -0.00000 -0.00000 4 -385.86432757 4.33336215 0.00207198 -0.19771 -0.00008 -0.00760 5 -385.86302032 4.36893239 0.00000000 0.00000 0.00000 0.00000 6 -385.83882683 5.02723716 0.05642531 0.95823 0.00041 0.02725 7 -385.83832257 5.04095814 0.00000000 -0.00000 -0.00000 -0.00000 ---- NOSI State Identification (Coefficients) ---- ================================================== State |0> = -0.697 |a2-Ax.B.mwfn> +0.697 |spin_flip_a2-Ax.B.mwfn> State |1> = -0.695 |a2-Ax.B.mwfn> -0.695 |spin_flip_a2-Ax.B.mwfn> +0.083 |a2-A+.B-.mwfn> +0.083 |spin_flip_a2-A+.B-.mwfn> State |2> = -0.684 |a2-A.Bx.mwfn> +0.684 |spin_flip_a2-A.Bx.mwfn> +0.130 |a2-A-.B+.mwfn> -0.130 |spin_flip_a2-A-.B+.mwfn> State |3> = -0.674 |a2-A.Bx.mwfn> -0.674 |spin_flip_a2-A.Bx.mwfn> +0.162 |a2-A-.B+.mwfn> +0.162 |spin_flip_a2-A-.B+.mwfn> State |4> = -0.190 |a2-A.Bx.mwfn> +0.190 |spin_flip_a2-A.Bx.mwfn> -0.697 |a2-A-.B+.mwfn> +0.697 |spin_flip_a2-A-.B+.mwfn> State |5> = -0.220 |a2-A.Bx.mwfn> -0.220 |spin_flip_a2-A.Bx.mwfn> -0.690 |a2-A-.B+.mwfn> -0.690 |spin_flip_a2-A-.B+.mwfn> State |6> = +0.705 |a2-A+.B-.mwfn> -0.705 |spin_flip_a2-A+.B-.mwfn> State |7> = +0.139 |a2-Ax.B.mwfn> +0.139 |spin_flip_a2-Ax.B.mwfn> +0.704 |a2-A+.B-.mwfn> +0.704 |spin_flip_a2-A+.B-.mwfn> --omitted-- ---- NOSI Results ---- ====================== State NOSI Energies Excited Energy Osc. Str. DX DY DZ (Hartree) (eV) (a.u.) (a.u.) (a.u.) 0 -386.12737900 0.00000000 0.00000000 0.69404 -0.00130 0.01149 1 -386.02210988 2.86437281 0.00000000 0.00002 -0.00005 0.00002 2 -386.00487812 3.33324890 0.00160706 -0.00014 0.19868 0.00014 ---- NOSI State Identification (Coefficients) ---- ================================================== State |0> = -1.000 |a2-AB.mwfn> State |1> = +0.707 |a2-ABx.mwfn> -0.707 |spin_flip_a2-ABx.mwfn> State |2> = +0.707 |a2-ABx.mwfn> +0.707 |spin_flip_a2-ABx.mwfn> ---- NOSI State Identification (Weights) ---- ============================================= State |0> = 1.000 |a2-AB.mwfn> State |1> = 0.500 |a2-ABx.mwfn> 0.500 |spin_flip_a2-ABx.mwfn> State |2> = 0.500 |a2-ABx.mwfn> 0.500 |spin_flip_a2-ABx.mwfn> --omitted-- MS-EDA Results ============== E[A]+E[B] = -386.11739232 Hartree -> 0.00000 eV (As reference) E[A.B] = -386.12242778 Hartree -> -0.13702 eV E[A+.B-] = -385.84489824 Hartree -> 7.41494 eV E[A-.B+] = -385.87243970 Hartree -> 6.66550 eV E[Ax.B] = -386.01250458 Hartree -> 2.85414 eV E[A.Bx] = -385.96335089 Hartree -> 4.19168 eV E[AB] = -386.12737901 Hartree -> -0.27175 eV E[ABx] = -386.01349416 Hartree -> 2.82721 eV delta E_Lint = E[A.B]-(E[A]+E[B]) = -0.00503546 Hartree = -0.13702 eV delta E_exciton = E[exciton]-E[A.B] delta delta E_superexchange = E[SE]-E[exciton] delta delta E_OCD = E[es]-E[SE] .. tab:: (C\ :sub:`6`\ H\ :sub:`6`\ )-(cis-2-butadiene) .. code-block:: :caption: da.inp :linenos: ---- NOSI Results ---- ====================== State NOSI Energies Excited Energy Osc. Str. DX DY DZ (Hartree) (eV) (a.u.) (a.u.) (a.u.) 0 -389.17311402 0.00000000 0.00000000 -49.44221 32.46889 175.72001 1 -389.13014230 1.16926051 0.00000022 -0.00221 0.00104 -0.00311 2 -389.04224936 3.56082738 0.00000000 -0.00000 -0.00000 -0.00000 3 -388.98001080 5.25433883 0.00000000 0.00000 -0.00000 -0.00000 ---- NOSI State Identification (Coefficients) ---- ================================================== State |0> = +0.707 |da-A.Bx.mwfn> -0.707 |spin_flip_da-A.Bx.mwfn> State |1> = -0.707 |da-Ax.B.mwfn> +0.707 |spin_flip_da-Ax.B.mwfn> State |2> = +0.703 |da-Ax.B.mwfn> +0.703 |spin_flip_da-Ax.B.mwfn> State |3> = -0.703 |da-A.Bx.mwfn> -0.703 |spin_flip_da-A.Bx.mwfn> --omitted-- ---- NOSI Results ---- ====================== State NOSI Energies Excited Energy Osc. Str. DX DY DZ (Hartree) (eV) (a.u.) (a.u.) (a.u.) 0 -389.17333875 0.00000000 0.00000000 -49.45653 32.46933 175.73035 1 -389.13050228 1.16558039 0.00001142 0.01954 0.00112 -0.02047 2 -389.04660899 3.44831695 0.00000000 -0.00000 -0.00000 0.00000 3 -389.03138698 3.86250786 0.00840862 -0.34847 -0.01060 0.23810 4 -389.02868531 3.93602011 0.00000000 0.00000 0.00000 -0.00000 5 -388.98027936 5.25314614 0.00000000 -0.00000 -0.00000 0.00000 6 -388.97047941 5.51980273 0.00000000 0.00000 -0.00000 0.00000 7 -388.96978161 5.53879003 0.00161774 -0.13448 -0.01237 0.07533 ---- NOSI State Identification (Coefficients) ---- ================================================== State |0> = +0.706 |da-A.Bx.mwfn> -0.706 |spin_flip_da-A.Bx.mwfn> State |1> = -0.705 |da-Ax.B.mwfn> +0.705 |spin_flip_da-Ax.B.mwfn> State |2> = +0.600 |da-Ax.B.mwfn> +0.600 |spin_flip_da-Ax.B.mwfn> +0.097 |da-A.Bx.mwfn> +0.097 |spin_flip_da-A.Bx.mwfn> +0.342 |da-A-.B+.mwfn> +0.342 |spin_flip_da-A-.B+.mwfn> State |3> = +0.706 |da-A-.B+.mwfn> -0.706 |spin_flip_da-A-.B+.mwfn> State |4> = +0.369 |da-Ax.B.mwfn> +0.369 |spin_flip_da-Ax.B.mwfn> -0.610 |da-A-.B+.mwfn> -0.610 |spin_flip_da-A-.B+.mwfn> State |5> = -0.635 |da-A.Bx.mwfn> -0.635 |spin_flip_da-A.Bx.mwfn> +0.282 |da-A+.B-.mwfn> +0.282 |spin_flip_da-A+.B-.mwfn> State |6> = -0.292 |da-A.Bx.mwfn> -0.292 |spin_flip_da-A.Bx.mwfn> -0.647 |da-A+.B-.mwfn> -0.647 |spin_flip_da-A+.B-.mwfn> State |7> = -0.708 |da-A+.B-.mwfn> +0.708 |spin_flip_da-A+.B-.mwfn> --omitted-- ---- NOSI Results ---- ====================== State NOSI Energies Excited Energy Osc. Str. DX DY DZ (Hartree) (eV) (a.u.) (a.u.) (a.u.) 0 -389.30494836 0.00000000 0.00000000 -49.31280 32.52416 175.77907 1 -389.14670530 4.30579375 0.00000000 -0.00000 0.00000 0.00000 2 -389.01536102 7.87967170 0.49201856 -0.66872 2.07558 -0.59758 ---- NOSI State Identification (Coefficients) ---- ================================================== State |0> = -1.000 |da-AB.mwfn> State |1> = -0.707 |da-ABx.mwfn> +0.707 |spin_flip_da-ABx.mwfn> State |2> = +0.707 |da-ABx.mwfn> +0.707 |spin_flip_da-ABx.mwfn> --omitted-- MS-EDA Results ============== E[A]+E[B] = -389.30025849 Hartree -> 0.00000 eV (as reference) E[A.B] = -389.30313645 Hartree -> -0.07831 eV E[A+.B-] = -388.97113637 Hartree -> 8.95587 eV E[A-.B+] = -389.03260717 Hartree -> 7.28316 eV E[Ax.B] = -389.08586649 Hartree -> 5.83390 eV E[A.Bx] = -389.07689636 Hartree -> 6.07799 eV E[AB] = -389.30494829 Hartree -> -0.12762 eV E[ABx] = -389.08103350 Hartree -> 5.96542 eV delta E_Lint = E[A.B]-(E[A]+E[B]) = -0.00287796 Hartree = -0.07831 eV delta E_exciton = E[exciton]-E[A.B] delta delta E_superexchange = E[SE]-E[exciton] delta delta E_OCD = E[es]-E[SE] For ``tn.out``, we list the results of TSO-DFT for the diabatic and dibatic excited states. The ``E[exciton]``, ``E[SE]``, and ``E[es]`` have to be selected from the NOSI energies, like shown in Line 5-8, 21-28, and 45-47. In most cases, you should choose the **lowest singlet states**, where the coefficients of the wave function and its spin-flip one have **the same sign.** The selected states are highlighted. For example, for ``exciton``, we choose ``State 2`` (Line 14), it is a combination of local exciton state [A*][B] and [A][B*], its energy is given in Line 7. For ``SE``, we choose ``State 1`` (Line 33), it is a state of [A\ :sup:`-`\ ][B\ :sup:`+`\ ] and has little contributions from other states. For ``es``, we choose ``State 3`` (Line 47), it is the target excited state. .. tip:: In principle, you can choose other intermediate excited states to see the SE or exciton effects, but you should be absolutely sure what you intend to do. Now we can do the calculations accoding to the equations given in Line 66-69. - delta E_Lint = E[A.B]-(E[A]+E[B]) = -0.23 eV - delta E_exciton = E[exciton]-E[A.B] = (-640.25510627--640.45105170)*27.21 = +5.33 eV - delta delta E_superexchange = E[SE]-E[exciton] = (-640.34091881--640.25510627)*27.21 = -2.33 eV - delta delta E_OCD = E[es]-E[SE] = (-640.33525702--640.34091881)*27.21 = +0.15 eV For other exciplexes, the calculations are done in the same way. The results are shown below: .. list-table:: :stub-columns: 1 * - Type - (MeOCH=CH\ :sub:`2`\ )(TCNE) - acetone dimer - (C\ :sub:`6`\ H\ :sub:`6`\ )-(cis-2-butadiene) * - :math:`\Delta E_{\text{Lint}}` - -0.23 eV - -0.14 eV - -0.08 eV * - :math:`\Delta E_{\text{exciton}}` - +5.33 eV - +3.24 eV - +7.10 eV * - :math:`\Delta \Delta E_{\text{superexchange}}` - -2.33 eV - -0.06 eV - -0.12 eV * - :math:`\Delta \Delta E_{\text{OCD}}` - +0.15 eV - +0.02 eV - +0.85 eV We can see that: - (MeOCH=CH\ :sub:`2`\ )(TCNE) has a very large :math:`\Delta\Delta E_{\text{superexchange}}`, so it is a **charge transfer excipler**; - Acetone dimer has very small :math:`\Delta\Delta E_{\text{superexchange}}` and :math:`\Delta\Delta E_{\text{OCD}}`, so it is an **encounter excipler**; - (C\ :sub:`6`\ H\ :sub:`6`\ )-(cis-2-butadiene) has a large :math:`\Delta E_{\text{OCD}}`, so it is a **intimate excipler**. This is not unexpected, since a Dield-Alder reaction is about to occur between the two fragments upon photochemical ways, thus there should be considerable orbital overlap, leading to a large :math:`\Delta\Delta E_{\text{OCD}}`. Besides the output file, you can also find some MWFN files corresponding to the diabatic (``tn-A.B.mwfn``), dibatic excited (``tn-Ax.B.mwfn``, ``tn-A.Bx.mwfn``), charge-transfer (``tn-A+.B-.mwfn``, ``tn-A-.B+.mwfn``), and standard ground (``tn-AB.mwfn``) and excited state (``tn-ABx.mwfn``).