Applications of ETS-NOCV Method in a Description of Chemical Reactions

Supporting information

Applications of ETS-NOCV method in a description of chemical reactions

Mariusz P. Mitoraj[1], Monika Parafiniuk, Monika Srebro, Michał Handzlik, Agnieszka Buczek, Artur Michalak

Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R.Ingardena 3, 30-060 Krakow, Poland

1. The optimized geometries of the structures reported in the paper – pages 2–5.
2. NOCV eigenvalues, q(k), and corresponding orbital interaction energies, Eorb(k) characterizing dominating deformation density contributions, (k) for i-S, i-TS, i-P (i=1,4), page 6.
3. ETS energy decomposition results describing the bond between ethene and 1,3-butadiene for II-S, II-TS, II-P when the triplet spin states for reactants are used. In addition NOCV-deformation densities are shown,page 7.
4. The selected geometrical parameters for the reactions under study (distances are in Å unit), page 8.
5. ETS energy decomposition results describing the interaction between two closed shell fragments NH3BH3 and Ir-catalyst, page 9.
6. ETS energy decomposition results describing the interaction between three closed shell fragments H+, NH3BH2- and Ir-containing catalyst in the case of reaction IV, page 10.
7. ETS energy decomposition results describing the bond between ethylene and Ti-based fragment for III-S and III-TS and III-P. Fragments in triplet spin state were considered. The dominating contributions to the deformation density describing the bond between ethylene and titanium-based fragments for the III-S and III-TS structures according to the ETS-NOCV analysis. Triplet fragments were considered, page 11.
8. ETS energy decomposition results describing the bond between hydrogen and CN unit for I-S, I-TS, I-P. Additionally excited state of CN was used for the transition state, page 12.

1. The optimized geometries of the structures reported in the paper (the atomic symbol followed by three cartesian coordinates, in Å).

The structures labels correspond to those of Figure 1.

1

I-S

H-0.997493 0.006131 0.00000

C0.075615 0.0020570.00000

N1.23502-0.0023450.00000

I-TS

H0.142500.99477 0.00000

C0.03513-0.205120.00000

N1.187670.10418 0.00000

I-P

H1.927730.75886 0.00000

C0.04207-0.35413 0.00000

N1.053240.24886 0.00000

II-TS

C -0.000184 0.000119 0.001027

C 1.381350 0.000166 -0.001008

C 2.126938 1.192638 -0.000537

C 1.521854 2.434757 -0.000451

H -0.555392 0.799264 0.489777

H -0.547566 -0.936087 -0.123730

H 1.908912 -0.933054 -0.218359

H 3.196677 1.127411 -0.217668

H 2.123653 3.338013 -0.124222

H 0.560939 2.581698 0.490648

C -0.472008 1.172341 -1.901662

C 0.262791 2.346009 -1.900710

H -1.528850 1.190216 -1.629846

H -0.153048 0.327106 -2.511224

H -0.216930 3.288188 -1.630638

H 1.161680 2.429633 -2.511429

II-P

C -0.097247 0.144161 -0.305695

C 1.380542 0.040964 -0.054857

C 2.089944 1.177036 -0.053022

C 1.349266 2.459374 -0.305023

H -0.577891 0.628934 0.567343

H -0.569197 -0.843160 -0.413208

H 1.846036 -0.932249 0.113625

H 3.169509 1.184425 0.116771

H 2.030111 3.316234 -0.412890

H 0.702534 2.678217 0.567282

C -0.364419 1.007130 -1.557485

C 0.460138 2.319121 -1.558976

H -1.442824 1.222436 -1.629461

H -0.098267 0.406184 -2.441191

H -0.201096 3.195261 -1.638073

H 1.121116 2.335197 -2.439212

III-S

C 0.041027 0.012590 -0.063008

C 1.468606 0.047498 -0.050930

C 1.874770 1.413448 -0.008938

C 0.688558 2.230961 0.003062

C -0.433522 1.367568 -0.056478

Ti 0.777526 0.939966 2.028511

C 0.625151 2.766445 3.215601

C 2.101326 2.807737 2.969291

C 2.968255 2.654690 4.217610

C 2.364707 -1.140040 -0.189675

C 3.276620 1.910519 -0.183498

C 0.637864 3.721308 -0.115846

C -1.847891 1.825417 -0.221328

C -0.774657 -1.225594 -0.264198

O 1.676634 -0.342154 2.947378

C 2.607548 -1.296149 3.223407

C 2.191134 -2.598683 3.554288

C 3.175045 -3.564026 3.787682

C 4.532136 -3.247001 3.722199

C 4.925762 -1.943927 3.414029

C 3.965901 -0.970281 3.161252

C 0.755678 -2.948778 3.680785

C 0.165391 -3.864559 2.801881

C -1.173132 -4.227725 2.951773

C -1.933148 -3.686199 3.990917

C -1.346420 -2.786280 4.881122

C -0.011900 -2.417856 4.726048

H 2.388691 3.686287 2.369919

H 0.036787 3.535281 2.697559

H 0.374782 2.726173 4.280724

H 2.449849 1.973029 2.254352

H 2.858362 -4.573604 4.055265

H 5.280872 -4.014838 3.924883

H 4.257158 0.051653 2.918668

H 5.983760 -1.683621 3.373191

H 1.951412 -2.026569 0.310637

H 2.487882 -1.387029 -1.258216

H 3.364556 -0.959925 0.226661

H 3.491290 2.018036 -1.260972

H 3.434889 2.896214 0.274539

H 4.017501 1.211325 0.227132

H -0.286454 4.136229 0.308181

H 1.489245 4.213380 0.372568

H 0.667610 4.011300 -1.180654

H -2.560361 0.991824 -0.191314

H -2.144849 2.565273 0.536885

H -1.961938 2.308949 -1.206322

H 0.461034 -1.745037 5.443676

H -1.928178 -2.384779 5.711853

H -2.976303 -3.980900 4.117313

H 0.766032 -4.304624 2.003174

H -1.620406 -4.947429 2.264667

H -0.398801 -2.067672 0.333916

H -1.832716 -1.079668 -0.014191

H -0.727151 -1.526517 -1.325046

H 2.800321 3.513962 4.883530

H 2.710508 1.737929 4.767033

H 4.038126 2.618523 3.968940

C -1.252929 0.917045 3.645858

C -1.473204 0.060082 2.618135

H -1.780339 1.868144 3.719440

H -0.671328 0.607956 4.516551

H -2.199857 0.302512 1.844211

H -1.092996 -0.966359 2.655247

III-TS

C -0.015092 0.146954 0.048715

C 1.509930 0.129198 0.006362

C 2.145092 1.506952 0.080400

H 1.472450 2.246590 -0.361282

H 3.126288 1.568301 -0.414848

H -0.428730 -0.869186 -0.010682

H -0.384680 0.611777 0.973606

H -0.403783 0.720082 -0.806306

H 1.890719 -0.375282 -0.899070

H 1.867014 -0.608710 0.791460

Ti 2.782312 0.630787 2.090294

O 1.352195 0.287964 3.159328

C 0.545104 -0.392803 4.016702

C -0.068543 -1.573424 3.585138

H 0.087848 -1.907847 2.559677

C -0.869001 -2.302281 4.457295

H -1.352146 -3.216791 4.112414

C -1.053924 -1.857770 5.766641

H -1.684165 -2.421042 6.454753

C -0.448144 -0.676482 6.188221

H -0.616301 -0.305818 7.200645

C 0.350169 0.085224 5.327387

C 0.946550 1.356065 5.799127

C 1.810432 1.368471 6.900853

H 2.068756 0.427436 7.390411

C 2.330225 2.570337 7.380410

H 2.998141 2.565353 8.242678

C 1.983281 3.775487 6.772144

H 2.378247 4.716740 7.156289

C 1.108337 3.774609 5.685458

H 0.809206 4.717404 5.225653

C 0.596166 2.573498 5.199780

H -0.119854 2.574262 4.376318

H 6.042096 2.486383 1.759969

C 6.084703 1.533953 1.215276

H 5.853153 1.732927 0.159965

H 7.131521 1.186381 1.258007

C 5.189535 0.493378 1.806496

C 4.601607 -0.587815 1.102900

C 4.872637 0.344776 3.197116

C 4.108554 -0.852329 3.348698

C 3.917702 -1.420824 2.056141

C 3.687305 -1.450048 4.650890

H 2.775503 -2.056190 4.559924

H 3.507342 -0.676977 5.410222

H 4.488430 -2.108725 5.028938

C 4.795632 -0.894303 -0.349152

H 4.012271 -1.553191 -0.745738

H 4.835744 0.010833 -0.971657

H 5.756711 -1.419496 -0.487172

C 5.413599 1.161014 4.326490

H 5.798323 2.132276 3.991114

H 4.659832 1.342044 5.106343

H 6.254280 0.622205 4.796531

C 3.290446 -2.751159 1.775323

H 2.489884 -2.984623 2.489992

H 2.876558 -2.816004 0.759216

H 4.051823 -3.545204 1.864564

C 2.316040 3.011218 1.610973

H 2.720640 3.622563 0.803085

H 1.240236 3.119375 1.767963

C 3.141302 2.716233 2.711530

H 4.181465 3.039544 2.675836

H 2.687103 2.656220 3.707314

III-P

C 0.001339 -0.012650 -0.002083

C 1.433903 -0.008067 -0.002726

C 1.872580 1.350171 0.005799

C 0.718390 2.186553 -0.007731

C -0.441222 1.342297 0.016049

Ti 0.606803 0.954704 -2.028658

O -0.994767 1.183637 -2.863636

C -2.346330 1.181582 -3.013930

C -3.027744 -0.039829 -3.029696

C -4.410784 -0.065090 -3.167634

C -5.118642 1.131667 -3.280500

C -4.434505 2.344527 -3.267753

C -3.040875 2.401421 -3.143797

C -2.349314 3.709527 -3.152095

C -2.744799 4.720580 -2.266142

C -2.136353 5.974240 -2.300666

C -1.131981 6.238532 -3.230372

C -0.742549 5.243549 -4.127415

C -1.342584 3.987602 -4.086525

C 3.286488 1.812344 0.144611

C 2.308412 -1.215713 0.145249

C 0.702969 3.677172 0.081640

C -1.849649 1.807804 0.187198

C -0.877249 -1.222130 0.072869

C 2.713974 -0.290322 -3.318055

C 2.913080 0.810047 -4.363553

C 1.484341 -1.191351 -3.506524

H 2.936130 0.367516 -5.373225

H 3.900608 1.270832 -4.195619

H 1.438197 -1.979781 -2.741780

H 0.495556 -0.675838 -3.539798

H 1.520017 -1.684558 -4.491634

H 3.600959 -0.944358 -3.273246

H 2.725348 0.188750 -2.306812

H -2.459360 -0.966301 -2.941678

H -4.935317 -1.020451 -3.193582

H -6.202177 1.120223 -3.398085

H -4.981004 3.280721 -3.390766

H -3.540914 4.521524 -1.546046

H -2.458505 6.751446 -1.606683

H -0.666555 7.224096 -3.269521

H 0.018134 5.456809 -4.879605

H -1.064814 3.224023 -4.813681

H 3.436057 2.817004 -0.273883

H 4.004386 1.128071 -0.332053

H 3.549993 1.863260 1.217084

H -2.580704 1.112216 -0.246777

H -2.008758 2.796842 -0.262522

H -2.070153 1.891535 1.265770

H 1.847508 -2.120772 -0.274976

H 3.297671 -1.082676 -0.314834

H 2.475348 -1.412201 1.219500

H 1.636889 4.119992 -0.286803

H -0.129443 4.114543 -0.487964

H 0.580991 3.982819 1.135361

H -1.868701 -1.031782 -0.358725

H -0.439288 -2.090585 -0.438970

H -1.028438 -1.510556 1.127458

C 1.702243 2.516406 -2.879581

C 1.831997 1.893230 -4.280488

H 2.051425 2.690772 -5.014451

H 0.864165 1.477207 -4.624908

H 2.681156 2.775268 -2.446829

H 1.057821 3.412170 -2.894021

IV-S

Ir 0.124574 -0.030391 0.040293

P 0.958866 -1.009060 1.930671

P 0.087093 0.655813 -2.148555

P 1.590133 1.440871 0.986439

P -0.402675 -1.855577 -1.253135

C 2.216461 0.295536 2.297524

H 3.223206 -0.049381 2.075034

H 2.198525 0.690394 3.310334

C -0.201474 -1.013962 -2.888666

H 0.669583 -1.375979 -3.429065

H -1.069106 -1.077349 -3.540312

H 1.208901 1.182698 -2.802546

H 0.385549 -3.012460 -1.311208

H 1.648450 -2.229229 1.914704

H 2.721001 1.914594 0.306322

H 0.256168 -1.174634 3.137151

H 1.264866 2.618585 1.685322

H -1.679739 -2.438721 -1.297676

H -0.907237 1.473394 -2.711958

H -1.567313 0.565196 0.619019

H -2.906979 0.159403 -0.914508

B -2.704886 0.109414 0.271612

H -2.943980 -0.952985 0.775232

N -3.712912 1.182367 0.946360

H -4.672393 0.930017 0.744375

H -3.614469 1.210348 1.952289

H -3.565191 2.119047 0.595198

IV-TS

Ir 6.213577 2.965162 4.112390

P 6.722524 2.097636 6.177479

P 5.978671 3.697224 1.948129

P 8.160682 4.003421 4.856375

P 6.225511 1.097447 2.730592

C 8.237790 3.101849 6.481485

H 9.136448 2.502024 6.600882

H 8.149950 3.761115 7.341448

C 5.865529 2.033028 1.165925

H 6.571895 1.861039 0.358246

H 4.862891 1.827768 0.798921

H 4.930484 3.826646 4.667764

H 6.998044 4.374745 1.265890

H 7.307335 0.266229 2.393011

H 7.096757 0.759501 6.362965

H 9.451136 3.843374 4.322247

H 5.904344 2.262610 7.305380

H 8.288570 5.355824 5.217286

H 5.226779 0.110330 2.785973

H 4.865462 4.419520 1.492728

B 3.857260 2.779622 4.336848

H 3.443721 2.637795 3.213504

H 3.702026 1.824749 5.045922

N 2.821371 3.898938 4.962432

H 1.881883 3.524338 4.912352

H 3.009658 4.110477 5.933760

H 2.825795 4.773665 4.453798

IV-P

Ir -0.022777 0.183848 0.069049

B -2.149858 -0.425594 0.102305

H -2.622050 -0.641958 -0.999977

H -2.331089 -1.375377 0.828539

N -3.081599 0.755525 0.708461

H -4.053727 0.472124 0.733728

H -2.800624 0.990741 1.649956

H -3.016867 1.604613 0.164167

H -0.470213 1.560223 0.778232

P 0.367354 -0.628108 2.183736

P -0.483175 0.914927 -2.054654

P 2.215060 0.789441 0.710390

P 0.107136 -1.668664 -1.360063

C 1.942634 0.284364 2.481856

H 2.745920 -0.279487 2.947674

H 1.744883 1.167574 3.085592

C -0.416123 -0.737290 -2.876422

H 0.299817 -0.790270 -3.692198

H -1.386716 -1.060292 -3.241863

H 0.368729 1.739334 -2.803747

H 1.258517 -2.368203 -1.756792

H 0.665715 -1.978923 2.406720

H 3.390684 0.102932 0.364449

H -0.461612 -0.390667 3.289183

H 2.754471 2.081574 0.796309

H -0.789409 -2.738653 -1.245554

H -1.719729 1.476110 -2.402750

1

Table S1. NOCV eigenvalues, q(k), and corresponding orbital interaction energy, Eorb(k) characterizing dominating deformation density contributions, (k) for i-S, i-TS, i-P (i=1,4).

1the interaction between H↑ and CN↓ were considered.

2the interaction between closed shell ethene and 1,3-butadiene were considered.

3the interaction between closed shell ethene and Ti-based catalyst were considered.

4the interaction between three fragments were analyzed (H↑, NH3H2B↓ and closed shell Ir-catalyst).

Table S2. ETS energy decomposition results describing the bond between ethene and 1,3-butadiene for II-S, II-TS, II-P when the triplet spin states for reactants are used.

1)Distortion energy, ΔEdist, calculated with respect to the singlet ground state of ethene and 1,3-butadiene.

Figure S1. Deformation density contributions, 1 and 2, together with the corresponding energies for the transition state (II-TS) and product (II-P) whenethene and 1,3-butadiene in the triplet spin state are used.

Scheme S1. The selected bond lengths for the reactions under study (distances are in Å unit).

Table S3. ETS1,2)energy decomposition results describing the interaction between two closed shell fragments NH3BH3 and Ir-catalyst.

1)Etotal = Eorb+EPauli +Eelstat + Edist

2)kcal/mol

3)see the labeling explanation given in Figure 1.

Table S4. ETS1,2)energy decomposition results describing the interaction between three closed shell fragments H+, NH3BH2- and Ir-containing catalyst in the case of reaction IV.

1)Etotal = Eorb+ EPauli +Eelstat + Edist

2) kcal/mol

3)see the labeling explanation given in Figure 1.

Table S5. ETSenergy decomposition results describing the bond between ethylene and Ti-based fragment for III-S and III-TS and III-P. Fragments in triplet spin state were considered.

Figure S2. The dominating contributions to the deformation density  describing the bond

between ethylene and titanium-based fragments for the III-S and III-TS structures according to

the ETS-NOCV analysis. Triplet fragments were considered.

Table S6. ETS1,2)energy decomposition results describing the bond between hydrogen and CN unit for I-S, I-TS, I-P.

1)Etotal = Eorb + EPauli + Eelstat + Edist.

2) kcal/mol.

3) see the labeling explanation given in Figure 1.

4) excited state of CN was considered (1σ212σ23σ24σ25σ2 1π21π1 ). Distortion energy calculated with respect to the doublet ground state of CN.

1

[1] Corresponding author. E-mail: . Tel. +48 12 6632042