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Electronic Supporting Information

Microhydration around Protonated Biomolecular Building Blocks: Protonated Pyrimidine

Kuntal Chatterjee and Otto Dopfer*

Institut für Optik und Atomare Physik, TU Berlin, Hardenbergstr. 36, 10623 Berlin, Germany.

* Corresponding author: dopfer@physik.tu-berlin.de

Table S1. Experimental and theoretical (calculated at B3LYP-D3/aug-cc-pVTZ level) data of structural

parameters of neutral Pym and respective changes upon protonation (in Å and degree).

Figure S1. Optimized structures of various H+Pym isomers calculated at the B3LYP-D3/aug-cc-pVTZ level.

Relative energies (E0) and bond lengths are given in kJ mol-1 and Å, respectively.

Figure S2. Linear IR spectra of neutral Pym and various H+Pym isomers obtained at the B3LYP-D3/aug-cc-

pVTZ level.

Figure S3. NBO atomic charge distributions (in e) of W, W2, Pym, H+Pym, and selected H+Pym-Ln clusters

with L=W (n=1-4) and L=N2 (n=1) obtained at the B3LYP-D3/aug-cc-pVTZ level.

Figure S4. Orbital interaction energies (E(2) in kJ mol-1) between the σ* orbital of the X-H donor bond and the

lone pair of L involved in XH…L and W…W moiety (X=N/O, and L=W/N2) of H+Pym-Ln and W2 obtained from

the NBO analysis at the B3LYP-D3/aug-cc-pVTZ level.

Figure S5. NCI plots of H+Pym-Ln and W2 calculated at the B3LYP-D3/aug-cc-pVTZ level.

Figure S6. Optimized structures of various H+Pym-N2 isomers calculated at the B3LYP-D3/aug-cc-pVTZ

level. Binding energies (D0) and bond lengths are given in cm-1 and Å, respectively. Numbers in parentheses

correspond to relative energies (E0).

Figure S7. Linear IR spectra of H+Pym(C5)-N2(CH) and H+Pym(C5)-N2(π) obtained at the B3LYP-D3/aug-cc-

pVTZ level.

Figure S8. Optimized structure and IR spectrum of Pym-W calculated at the B3LYP-D3/aug-cc-pVTZ level.

Binding energies (D0) and bond lengths are given in cm-1 and Å, respectively.

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2020

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Table S1. Experimental and theoretical (calculated at B3LYP-D3/aug-cc-pVTZ level) data of structural

parameters of neutral Pym and respective changes upon protonation (in Å and degree).

a From electron diffraction data (L. Fernholt and C. Romming, C., Acta Chem. Scand. 1978, 32, 271-273). Numbers in

parentheses are from a recent and more reliable microwave study combined with CCSD(T) corrections (Z.N. Heim et al.,

J. Chem. Phys. 2020, 152, 104303). The latter values agree much better with our B3LYP-D3 data.

structural parameters Pym H+Pym

expa calc Calc

rN1C2 1.340 (1.33333(38)) 1.3327 1.3512

rN3C2 1.340 (1.33333(38)) 1.3327 1.3080

rN3C4 1.340 1.3335 1.3379

rN1C6 1.340 1.3335 1.3488

rC4C5 1.393 (1.38675(45)) 1.3878 1.3959

rC5C6 1.393 1.3878 1.3747

rC2H7 1.099 (1.08165(39)) 1.0837 1.0824

rC4H8 1.099 (1.08224(30)) 1.0841 1.0830

rC6H10 1.099 (1.08224(30)) 1.0841 1.0801

rC5H9 1.099 (1.07929(36)) 1.0804 1.0793

rN1H11 1.0148

< (N1C2N3) 127.6 126.9 122.2

< (C2N3C4) 115.5 116.1 117.9

< (N3C4C5) 122.3 122.2 122.7

< (C4C5C6) 116.8 116.7 117.4

< (N1C2H7) 116.2 (116.332(24)) 116.5 117.2

< (C5C4H8) 122.4 (121.261(38)) 121.2 121.0

< (C6C5H9) 121.6 (121.665(22)) 121.7 120.7

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Figure S1

4

Figure S2

5

Figure S3

6

Figure S4

7

Figure S5

8

Figure S6

9

Figure S7

10

Figure S8

11

Optimized cartesian coordinates (in Å) and energies (in Hartree) of all relevant structures

Pym C 0.00000000 0.00000000 -1.30772900

N 0.00000000 1.19231900 -0.71242700

C 0.00000000 1.18110000 0.62104800

C 0.00000000 0.00000000 1.34975300

C 0.00000000 -1.18110000 0.62104800

N 0.00000000 -1.19231900 -0.71242700

H 0.00000000 2.14598500 1.11524000

H 0.00000000 0.00000000 -2.39140000

H 0.00000000 0.00000000 2.43018300

H 0.00000000 -2.14598500 1.11524000

Sum of electronic and zero-point Energies= -264.346942

Sum of electronic and thermal Energies= -264.342759

Sum of electronic and thermal Enthalpies= -264.341815

Sum of electronic and thermal Free Energies= -264.373636

H+Pym(N)

C -1.17217600 0.61288500 0.00000000

N -1.22742600 -0.69392200 0.00000000

C -0.07252900 -1.36941000 0.00000000

C 1.17187400 -0.73688000 0.00000000

C 1.18334800 0.63773400 0.00000000

N 0.00000000 1.28497600 0.00000000

H -0.14890700 -2.44966000 0.00000000

H -2.08049500 1.20156400 0.00000000

H 2.09483000 -1.29637900 0.00000000

H 2.07902500 1.24142900 0.00000000

H -0.01557000 2.29968300 0.00000000

Sum of electronic and zero-point Energies= -264.686185

Sum of electronic and thermal Energies= -264.681869

Sum of electronic and thermal Enthalpies= -264.680925

Sum of electronic and thermal Free Energies= -264.713659

H+Pym(C2)

C 0.00000000 0.00000000 -1.29947400

N 0.00000000 1.23496600 -0.64723400

C 0.00000000 1.22285300 0.65983400

C 0.00000000 0.00000000 1.36997600

C 0.00000000 -1.22285300 0.65983400

N 0.00000000 -1.23496600 -0.64723400

H 0.00000000 2.17277100 1.18128100

H 0.00000000 0.00000000 2.45388800

H 0.00000000 -2.17277100 1.18128100

H -0.82603000 0.00000000 -2.04809500

H 0.82603000 0.00000000 -2.04809500

Sum of electronic and zero-point Energies= -264.582235

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Sum of electronic and thermal Energies= -264.577426

Sum of electronic and thermal Enthalpies= -264.576481

Sum of electronic and thermal Free Energies= -264.609481

H+Pym(C4)

C -1.19576400 0.63948400 0.00000000

N -0.05443200 1.40442200 0.00000000

C 1.12952400 0.82259100 0.00000000

C 1.22723400 -0.57526200 0.00000000

C 0.00000000 -1.32529700 0.00000000

N -1.23643200 -0.65912100 0.00000000

H 2.00531800 1.46011200 0.00000000

H -2.12815700 1.18949900 0.00000000

H 2.18387700 -1.08479800 0.00000000

H 0.00452200 -2.07550900 0.82491700

H 0.00452200 -2.07550900 -0.82491700

Sum of electronic and zero-point Energies= -264.577539

Sum of electronic and thermal Energies= -264.572517

Sum of electronic and thermal Enthalpies= -264.571573

Sum of electronic and thermal Free Energies= -264.605697

H+Pym(C5)

C 0.10504000 -1.33004600 0.00000000

N -0.05270200 -0.75301800 1.20887600

C -0.05270200 0.54833900 1.22680700

C 0.06857300 1.35523500 0.00000000

C -0.05270200 0.54833900 -1.22680700

N -0.05270200 -0.75301800 -1.20887600

H -0.15959300 1.04185800 2.18854000

H 0.37908800 -2.38038700 0.00000000

H -0.15959300 1.04185800 -2.18854000

H 0.98302900 1.97382400 0.00000000

H -0.71434100 2.13389800 0.00000000

Sum of electronic and zero-point Energies= -264.607915

Sum of electronic and thermal Energies= -264.602598

Sum of electronic and thermal Enthalpies= -264.601654

Sum of electronic and thermal Free Energies= -264.636623

H+Pym+-N2(H)

C 1.03096800 -0.78943700 0.00000000

N 0.85626100 -2.08691700 0.00000000

C -0.40009100 -2.54616300 0.00000000

C -1.51194600 -1.70261200 0.00000000

C -1.27727000 -0.34772100 0.00000000

N 0.00000000 0.08093000 0.00000000

H -0.51720300 -3.62272800 0.00000000

H 2.02937200 -0.37183400 0.00000000

H -2.51943900 -2.08945700 0.00000000

H -2.05133700 0.40559200 0.00000000

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H 0.19667400 1.08305400 0.00000000

N 0.59249900 3.10541900 0.00000000

N 0.81009200 4.17356400 0.00000000

Sum of electronic and zero-point Energies= -374.258165

Sum of electronic and thermal Energies= -374.250066

Sum of electronic and thermal Enthalpies= -374.249122

Sum of electronic and thermal Free Energies= -374.293445

H+Pym+-N2(π)

C 0.73498200 -0.87305000 1.02434000

N 0.82414700 0.38426600 1.37305800

C 0.98198600 1.29150500 0.40336700

C 1.05268000 0.94834500 -0.94719300

C 0.95816300 -0.38496300 -1.26694800

N 0.80465400 -1.27112800 -0.26371400

H 1.05292500 2.32458800 0.72019300

H 0.60314600 -1.64268400 1.77358700

H 1.17718400 1.69324900 -1.71809800

H 0.99921300 -0.77614200 -2.27273100

H 0.72727100 -2.25991100 -0.47672100

N -2.20815600 -0.05786600 -0.10214100

N -3.26730200 0.19756900 -0.05115100

Sum of electronic and zero-point Energies= -374.255103

Sum of electronic and thermal Energies= -374.246757

Sum of electronic and thermal Enthalpies= -374.245813

Sum of electronic and thermal Free Energies= -374.290818

H+Pym+-N2(C4/C5)

C -2.24868800 -0.98153900 0.00000000

N -1.05591600 -1.51829400 0.00000000

C 0.00000000 -0.69591900 0.00000000

C -0.12527800 0.69418800 0.00000000

C -1.39699600 1.21495700 0.00000000

N -2.43767500 0.35621900 0.00000000

H 0.97676400 -1.16154300 0.00000000

H -3.13268500 -1.60609800 0.00000000

H 0.74117500 1.33648000 0.00000000

H -1.62580500 2.27052400 0.00000000

H -3.38552900 0.71824900 0.00000000

N 3.27716200 0.34570100 0.00000000

N 4.36669300 0.39526900 0.00000000

Sum of electronic and zero-point Energies= -374.254399

Sum of electronic and thermal Energies= -374.245977

Sum of electronic and thermal Enthalpies= -374.245033

Sum of electronic and thermal Free Energies= -374.291111

H+Pym+(C5)-N2(π)

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C 0.64135300 1.34297100 0.00092200

N 0.88251900 0.79183200 1.20642400

C 1.00488100 -0.50251300 1.22447700

C 0.92990400 -1.31847300 -0.00081300

C 1.00543300 -0.50085900 -1.22496600

N 0.88304900 0.79345900 -1.20521500

H 1.17795100 -0.98237700 2.18323600

H 0.22192400 2.34410500 0.00150600

H 1.17895500 -0.97942300 -2.18429200

H 0.03180400 -1.96043800 -0.00144600

H 1.74137800 -2.06400400 -0.00113600

N -2.18614400 -0.16881700 -0.00041600

N -3.27105700 -0.05713400 -0.00016400

Sum of electronic and zero-point Energies= -374.177798

Sum of electronic and thermal Energies= -374.168524

Sum of electronic and thermal Enthalpies= -374.167580

Sum of electronic and thermal Free Energies= -374.214405

H+Pym+(C5)-N2(CH)

C -0.83567400 -2.26074400 0.00000000

N -0.74607300 -1.67601700 1.21357500

C -0.74607300 -0.37242400 1.22615800

C -0.79148300 0.43122900 0.00000000

C -0.74607300 -0.37242400 -1.22615800

N -0.74607300 -1.67601700 -1.21357500

H -0.68921100 0.12259200 2.19141200

H -0.99564900 -3.33393600 0.00000000

H -0.68921100 0.12259200 -2.19141200

H 0.08880300 1.11044700 0.00000000

H -1.60925900 1.16984500 0.00000000

N 1.93548400 2.49626300 0.00000000

N 2.78671100 3.17786200 0.00000000

Sum of electronic and zero-point Energies= -374.177294

Sum of electronic and thermal Energies= -374.167903

Sum of electronic and thermal Enthalpies= -374.166959

Sum of electronic and thermal Free Energies= -374.215790

H+Pym+-W(H)

C 1.16012400 -0.17451000 0.00000000

N 1.21518900 -1.48468800 0.00000000

C 0.05641400 -2.15196500 0.00000000

C -1.18263000 -1.51127900 0.00000000

C -1.18084400 -0.13527100 0.00000000

N 0.00000000 0.50873100 0.00000000

H 0.12499300 -3.23266100 0.00000000

H 2.07208100 0.40777100 0.00000000

H -2.10879500 -2.06506600 0.00000000

H -2.07207700 0.47496600 0.00000000

H 0.02134300 1.55031400 0.00000000

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O 0.02581400 3.23825000 0.00000000

H 0.06562000 3.81426100 0.77176200

H 0.06562000 3.81426100 -0.77176200

Sum of electronic and zero-point Energies= -341.157825

Sum of electronic and thermal Energies= -341.149952

Sum of electronic and thermal Enthalpies= -341.149007

Sum of electronic and thermal Free Energies= -341.190762

H+Pym+-W(C5/C6)

C 1.97105500 0.59505800 0.00000000

N 1.31495400 1.72522700 0.00000000

C -0.02418000 1.67100600 0.00000000

C -0.73026500 0.46983800 0.00000000

C 0.00000000 -0.69661900 0.00000000

N 1.34472600 -0.60317200 0.00000000

H -0.53969100 2.62320800 0.00000000

H 3.05326900 0.58768700 0.00000000

H -1.80799500 0.42014700 0.00000000

H -0.45659000 -1.67620600 0.00000000

H 1.90399100 -1.44929200 0.00000000

O -2.70801900 -1.99599400 0.00000000

H -3.20312700 -2.31383800 0.76303500

H -3.20312700 -2.31383800 -0.76303500

Sum of electronic and zero-point Energies= -341.146404

Sum of electronic and thermal Energies= -341.138330

Sum of electronic and thermal Enthalpies= -341.137386

Sum of electronic and thermal Free Energies= -341.179794

H+Pym+-W(π)

C 0.19879700 -0.16679200 1.25575300

N -0.26440700 -1.25884500 0.70417800

C -1.02240700 -1.12941700 -0.38887700

C -1.33352000 0.10831100 -0.95134300

C -0.83486200 1.22698300 -0.32926500

N -0.08413400 1.06017700 0.77547800

H -1.39167200 -2.04777800 -0.82795500

H 0.82949800 -0.21980400 2.13246100

H -1.94160600 0.19401200 -1.83849700

H -1.00685500 2.23897800 -0.66422200

H 0.31326500 1.86931300 1.23879400

O 2.25747700 -0.05421700 -0.74153500

H 2.88028800 0.48979500 -1.23570000

H 2.64901200 -0.93462800 -0.74780300

Sum of electronic and zero-point Energies= -341.145194

Sum of electronic and thermal Energies= -341.136946

Sum of electronic and thermal Enthalpies= -341.136002

Sum of electronic and thermal Free Energies= -341.179156

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H+Pym+-W(C4/C5)

C -1.30169100 -1.58194000 0.00000000

N 0.00588800 -1.61238700 0.00000000

C 0.65811600 -0.44243200 0.00000000

C 0.00000000 0.78980500 0.00000000

C -1.37314100 0.77326400 0.00000000

N -1.99739100 -0.42421900 0.00000000

H 1.73970900 -0.47437600 0.00000000

H -1.87313600 -2.50110300 0.00000000

H 0.56422500 1.70974400 0.00000000

H -1.99678900 1.65499300 0.00000000

H -3.01090100 -0.46078200 0.00000000

O 2.95541000 1.65921300 0.00000000

H 3.48721300 1.91093700 0.76282200

H 3.48721300 1.91093700 -0.76282200

Sum of electronic and zero-point Energies= -341.144947

Sum of electronic and thermal Energies= -341.136822

Sum of electronic and thermal Enthalpies= -341.135877

Sum of electronic and thermal Free Energies= -341.178344

H+Pym+-W2(l1)

C 0.93842400 -1.14702600 0.19448500

N 2.20100000 -1.26285000 -0.14604700

C 2.87912400 -0.13585000 -0.38526700

C 2.29904500 1.12818500 -0.28659000

C 0.97162200 1.18516400 0.07404600

N 0.31384800 0.03780800 0.30922500

H 3.91896300 -0.25143400 -0.66441400

H 0.34963500 -2.03148600 0.39805900

H 2.86105700 2.02807200 -0.48320900

H 0.40975400 2.10112400 0.18396800

H -0.70756100 0.06460700 0.58714000

O -2.24461800 0.14980000 0.97831300

H -2.99849500 0.06240600 0.35120100

H -2.60823200 0.16885500 1.86839200

O -4.23260800 -0.08747100 -0.83696700

H -4.74170800 -0.89123900 -0.98619100

H -4.79883000 0.64291200 -1.10800000

Sum of electronic and zero-point Energies= -417.621436

Sum of electronic and thermal Energies= -417.610492

Sum of electronic and thermal Enthalpies= -417.609548

Sum of electronic and thermal Free Energies= -417.660224

H+Pym+-W2(l2)

C 0.21888000 -0.76196000 -0.02676600

N 1.31842300 -1.47999000 -0.01244000

C 2.48217700 -0.82228200 0.00957400

C 2.56251300 0.56975600 0.01874200

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C 1.37715700 1.26975900 0.00293400

N 0.22332300 0.58343600 -0.02088600

H 3.37757900 -1.43113500 0.02072800

H -0.75245800 -1.24109100 -0.04232200

H 3.51100500 1.08385000 0.03790100

H 1.30958000 2.34771900 0.00912000

H -0.70850000 1.07257600 -0.03147800

O -2.28362600 1.46613900 0.03349600

H -2.79843100 2.23928600 -0.21438100

H -2.86141100 0.67917600 -0.00474700

O -3.25407900 -1.09961200 0.01274400

H -3.71727200 -1.49287600 -0.73593800

H -3.69504100 -1.44549400 0.79756500

Sum of electronic and zero-point Energies= -417.620528

Sum of electronic and thermal Energies= -417.609842

Sum of electronic and thermal Enthalpies= -417.608898

Sum of electronic and thermal Free Energies= -417.657756

H+Pym+-W2(H-C5/C6)

C 0.24875300 -1.81633800 0.00000000

N 1.55752200 -1.75562800 0.00000000

C 2.11894600 -0.53968900 0.00000000

C 1.37188000 0.63563200 0.00000000

C 0.00000000 0.51338800 0.00000000

N -0.53496500 -0.72038700 0.00000000

H 3.20142400 -0.51395300 0.00000000

H -0.25137500 -2.77570400 0.00000000

H 1.81982300 1.61679500 0.00000000

H -0.66623400 1.36356600 0.00000000

H -1.56661800 -0.83946400 0.00000000

O 0.16465600 3.55437400 0.00000000

H 0.13287400 4.14160500 0.76294500

H 0.13287400 4.14160500 -0.76294500

O -3.25743100 -1.08161600 0.00000000

H -3.82796900 -1.17118400 0.77132000

H -3.82796900 -1.17118400 -0.77132000

Sum of electronic and zero-point Energies= -417.616167

Sum of electronic and thermal Energies= -417.604397

Sum of electronic and thermal Enthalpies= -417.603453

Sum of electronic and thermal Free Energies= -417.655187

H+Pym+-W3(b1)

C -0.85093000 1.57612600 0.00000000

N -0.69653200 2.88134200 0.00000000

C 0.55552600 3.34909400 0.00000000

C 1.67137500 2.51412400 0.00000000

C 1.44023500 1.15616600 0.00000000

N 0.17478200 0.71029200 0.00000000

H 0.66566900 4.42631300 0.00000000

18

H -1.84629600 1.15249400 0.00000000

H 2.67573000 2.90849000 0.00000000

H 2.21915300 0.40765400 0.00000000

H -0.01896400 -0.35468900 0.00000000

O -0.21528000 -1.84220000 0.00000000

H -0.40834300 -2.37504600 0.79737200

H -0.40834300 -2.37504600 -0.79737200

O -0.69653200 -3.20149900 2.33256200

H -1.56178600 -3.45755300 2.66805900

H -0.06663300 -3.81399200 2.72630700

O -0.69653200 -3.20149900 -2.33256200

H -1.56178600 -3.45755300 -2.66805900

H -0.06663300 -3.81399200 -2.72630700

Sum of electronic and zero-point Energies= -494.082395

Sum of electronic and thermal Energies= -494.067948

Sum of electronic and thermal Enthalpies= -494.067003

Sum of electronic and thermal Free Energies= -494.127659

H+Pym+-W3(b2)

C 1.20905300 0.86865300 0.09893500

N 2.51506700 0.97236700 0.21147600

C 3.22786100 -0.15542000 0.13183600

C 2.64285000 -1.40546500 -0.06315500

C 1.27052000 -1.44765300 -0.17333900

N 0.57750300 -0.30253700 -0.08795300

H 4.30164700 -0.05263000 0.22673600

H 0.58149400 1.74973000 0.15239000

H 3.23450300 -2.30553600 -0.12673800

H 0.70347000 -2.35415700 -0.32724800

H -0.49483200 -0.28650600 -0.17116300

O -1.99137300 -0.01839900 -0.34985400

H -2.76159100 -0.56772600 -0.09747700

H -2.19837400 0.92078500 -0.21033700

O -4.06681200 -1.68955500 0.25909300

H -4.52473400 -1.79634700 1.09902300

H -4.68736600 -1.97023900 -0.42160100

O -1.69781100 2.74016200 -0.02249300

H -1.99425600 3.25118400 0.73903500

H -1.86169700 3.30427700 -0.78690600

Sum of electronic and zero-point Energies= -494.081671

Sum of electronic and thermal Energies= -494.067663

Sum of electronic and thermal Enthalpies= -494.066718

Sum of electronic and thermal Free Energies= -494.124683

H+Pym+-W3(l1)

C 1.43363400 1.02640500 0.49170300

N 2.59248800 1.55374700 0.16839900

C 3.51056800 0.73892000 -0.36087400

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C 3.27936100 -0.61886300 -0.57517700

C 2.04445200 -1.11102100 -0.21565500

N 1.14057300 -0.27248900 0.31540000

H 4.45996600 1.19011500 -0.62085900

H 0.65951100 1.64715300 0.92265100

H 4.03163500 -1.26237500 -1.00440000

H 1.74289400 -2.14180700 -0.33171200

H 0.17744800 -0.64220800 0.59650600

O -1.20707100 -1.24512500 0.92426000

H -1.50901800 -1.55554000 1.78225700

H -2.00830900 -1.07999200 0.35640100

O -3.22865600 -0.75256800 -0.68361100

H -3.92600000 -0.09123000 -0.49542400

H -3.64016600 -1.44924500 -1.20290200

O -5.12260100 1.16332400 -0.12896900

H -5.88562300 1.04058100 0.44503200

H -5.37522200 1.83804700 -0.76756200

Sum of electronic and zero-point Energies= -494.081293

Sum of electronic and thermal Energies= -494.067312

Sum of electronic and thermal Enthalpies= -494.066368

Sum of electronic and thermal Free Energies= -494.126187

H+Pym+-W3(l2)

C -0.53520900 0.64782000 -0.20694800

N -1.50870500 1.50911700 -0.00717100

C -2.73176800 1.01484300 0.20893200

C -3.00009500 -0.35281400 0.23166800

C -1.93998600 -1.20518700 0.01792400

N -0.72327000 -0.68296900 -0.20183100

H -3.52073300 1.73873800 0.37049400

H 0.47377200 1.00270000 -0.38061400

H -3.99344800 -0.73406200 0.41091400

H -2.01800000 -2.28262500 0.01651300

H 0.11788000 -1.31785800 -0.35905100

O 1.43417200 -2.16356400 -0.42405400

H 1.78933500 -2.67657800 -1.15548000

H 2.17751200 -1.67119200 0.00081300

O 3.10029000 -0.50091800 0.80450900

H 3.13308200 0.40585000 0.45227000

H 3.90275900 -0.65002100 1.31248700

O 2.60753100 2.00445600 -0.34980200

H 3.05439600 2.26094900 -1.16462900

H 2.61367600 2.79329600 0.20461300

Sum of electronic and zero-point Energies= -494.081140

Sum of electronic and thermal Energies= -494.067609

Sum of electronic and thermal Enthalpies= -494.066665

Sum of electronic and thermal Free Energies= -494.122943

H+Pym+-W4(r)

20

C -1.25951300 2.33688100 0.00000000

N -1.15525900 3.64804800 0.00000000

C 0.07812800 4.16214400 0.00000000

C 1.22440100 3.36969200 0.00000000

C 1.04353700 2.00388800 0.00000000

N -0.20288800 1.50943100 0.00000000

H 0.14807900 5.24274400 0.00000000

H -2.23785200 1.87506600 0.00000000

H 2.21319900 3.80154800 0.00000000

H 1.85186500 1.28692200 0.00000000

H -0.37274200 0.42409200 0.00000000

O -0.70350200 -1.00166900 0.00000000

H -0.49764000 -1.56535300 0.77819100

H -0.49764000 -1.56535300 -0.77819100

O 0.07812800 -2.80888500 1.87721800

H -0.32670600 -3.05238200 2.71493800

H 0.25290400 -3.63506000 1.39820700

O 0.07812800 -2.80888500 -1.87721800

H -0.32670600 -3.05238200 -2.71493800

H 0.25290400 -3.63506000 -1.39820700

O 0.65194900 -4.94075700 0.00000000

H 1.57026600 -5.23596900 0.00000000

H 0.12015800 -5.74522700 0.00000000

Sum of electronic and zero-point Energies= -570.542037

Sum of electronic and thermal Energies= -570.525842

Sum of electronic and thermal Enthalpies= -570.524897

Sum of electronic and thermal Free Energies= -570.588953

H+Pym+-W4(b1)

C 1.64131700 -0.62562800 -0.99607400

N 2.84540400 -1.11107800 -1.20666200

C 3.77823100 -0.84836600 -0.28636100

C 3.51686600 -0.09660800 0.85719000

C 2.23404000 0.38114000 1.01508400

N 1.31415300 0.10665900 0.07885700

H 4.76469300 -1.25404600 -0.47302900

H 0.85471300 -0.81412500 -1.71440600

H 4.28173600 0.10557600 1.59091000

H 1.90710300 0.97383600 1.85715700

H 0.28742700 0.48250100 0.19876600

O -1.04721700 0.99904900 0.45812800

H -1.40809000 1.79461000 0.02087300

H -1.78484000 0.38931700 0.70237600

O -1.87145600 3.32381500 -0.76606700

H -2.35519200 3.40369500 -1.59436500

H -2.08942800 4.10967000 -0.25434800

O -2.89377500 -0.78183600 1.18704800

H -3.53264000 -1.22714100 0.59636900

H -3.30248600 -0.74593400 2.05629100

O -4.63376400 -2.07407600 -0.53807400

21

H -5.50363100 -1.75106200 -0.79410000

H -4.68928400 -3.03481400 -0.56517100

Sum of electronic and zero-point Energies= -570.541108

Sum of electronic and thermal Energies= -570.523586

Sum of electronic and thermal Enthalpies= -570.522642

Sum of electronic and thermal Free Energies= -570.592384

H+Pym+-W4(b2)

C 1.21516800 -0.91637700 0.16543700

N 2.33041900 -1.58924300 -0.02445100

C 3.43837800 -0.88185800 -0.26406000

C 3.44854200 0.51079600 -0.31625200

C 2.24901100 1.15594800 -0.11006800

N 1.15039700 0.42501100 0.12605400

H 4.34719300 -1.45015800 -0.41823700

H 0.28543400 -1.43379500 0.36991900

H 4.35390800 1.06528600 -0.50867300

H 2.12994000 2.22961400 -0.12460700

H 0.18411500 0.88866900 0.29662400

O -1.21312300 1.31422500 0.65541000

H -1.74695600 2.01573600 0.23340000

H -1.74894900 0.50189900 0.75674700

O -2.55795400 3.43800400 -0.45784300

H -3.05566500 3.49119400 -1.27982800

H -2.91866300 4.12066200 0.11744900

O -2.01904900 -1.27178500 0.96757500

H -2.61140300 -1.75888300 0.35859600

H -2.26881700 -1.54995000 1.85439000

O -3.63090000 -2.62646500 -0.81690200

H -3.48026200 -3.54261900 -1.07163300

H -4.57397600 -2.47092200 -0.93162500

Sum of electronic and zero-point Energies= -570.541411

Sum of electronic and thermal Energies= -570.524168

Sum of electronic and thermal Enthalpies= -570.523224

Sum of electronic and thermal Free Energies= -570.590293

H+Pym+-W4(l)

C -0.66502100 0.49645300 -0.37042300

N -1.12675100 1.72646000 -0.28290900

C -2.40761200 1.87965000 0.06528100

C -3.25148200 0.80396200 0.33659300

C -2.71253000 -0.45828000 0.22938800

N -1.42527300 -0.58532000 -0.12775500

H -2.76927100 2.89831300 0.13052600

H 0.37095100 0.32323300 -0.64226500

H -4.28250200 0.94748000 0.62037100

H -3.25989300 -1.37047600 0.41736600

H -0.98735300 -1.55621000 -0.20704300

O -0.28042800 -2.94501300 -0.16067200

22

H -0.27331800 -3.62086400 -0.84442700

H 0.65045600 -2.81228500 0.15185500

O 2.07595100 -2.13023900 0.69434300

H 2.42708200 -1.37567900 0.17885000

H 2.81430300 -2.57176600 1.12201300

O 2.56393100 0.09349200 -0.83259300

H 3.01276600 -0.00310500 -1.67834900

H 2.96524300 0.87749000 -0.40146400

O 3.58794300 2.28837200 0.46014400

H 4.39314100 2.29300600 0.98779400

H 3.44325800 3.19927900 0.18461000

Sum of electronic and zero-point Energies= -570.541297

Sum of electronic and thermal Energies= -570.524604

Sum of electronic and thermal Enthalpies= -570.523660

Sum of electronic and thermal Free Energies= -570.588801

W

O 0.00000000 0.00000000 0.11698300

H 0.00000000 0.76357100 -0.46793200

H 0.00000000 -0.76357100 -0.46793200

Sum of electronic and zero-point Energies= -76.444969

Sum of electronic and thermal Energies= -76.442134

Sum of electronic and thermal Enthalpies= -76.441190

Sum of electronic and thermal Free Energies= -76.462611

W2

O -0.00046000 1.51528100 0.00000000

H -0.09745200 0.55058300 0.00000000

H -0.89658900 1.86167300 0.00000000

O -0.00046000 -1.39401700 0.00000000

H 0.50070000 -1.69118200 0.76617600

H 0.50070000 -1.69118200 -0.76617600

Sum of electronic and zero-point Energies= -152.894964

Sum of electronic and thermal Energies= -152.889139

Sum of electronic and thermal Enthalpies= -152.888195

Sum of electronic and thermal Free Energies= -152.921231

W3

O -1.33503600 -0.90482900 -0.09589900

H -1.21731700 0.06147900 -0.02262000

O -0.12109400 1.60263300 0.11221300

H 0.66139700 1.02168800 0.05785900

H -0.04406700 2.22297300 -0.61772100

O 1.45727700 -0.69154800 -0.08757800

H 0.57180300 -1.09900700 -0.05049600

H -1.95565900 -1.15349400 0.59394000

H 1.97467100 -1.10368800 0.60915400

23

Sum of electronic and zero-point Energies= -229.352769

Sum of electronic and thermal Energies= -229.345314

Sum of electronic and thermal Enthalpies= -229.344370

Sum of electronic and thermal Free Energies= -229.382124

W4

O -1.36671600 -1.36671600 -0.00272400

H -0.39208700 -1.50195000 0.00951700

O 1.36671600 1.36671600 -0.00272400

H 0.39208700 1.50195000 0.00951700

O -1.36671600 1.36671600 0.00272400

H -1.50195000 0.39208700 -0.00951700

O 1.36671600 -1.36671600 0.00272400

H 1.50195000 -0.39208700 -0.00951700

H 1.86068400 -1.69622500 0.75812000

H 1.69622500 1.86068400 -0.75812000

H -1.69622500 -1.86068400 -0.75812000

H -1.86068400 1.69622500 0.75812000

Sum of electronic and zero-point Energies= -305.813843

Sum of electronic and thermal Energies= -305.804211

Sum of electronic and thermal Enthalpies= -305.803267

Sum of electronic and thermal Free Energies= -305.846308

Pym-W

C -0.43138700 -1.26067200 0.00592000

N -1.73961300 -1.01978900 -0.01728300

C -2.10083300 0.26434900 -0.01684100

C -1.17193900 1.29558800 0.00648600

C 0.16520600 0.93037600 0.03131100

N 0.54190000 -0.35075600 0.03163500

H -3.16515800 0.46835600 -0.03606100

H -0.12522300 -2.29985000 0.00340700

H -1.47487000 2.33232800 0.00523500

H 0.96200900 1.66416500 0.05048900

O 3.37453700 0.09566900 -0.09459500

H 2.48636600 -0.29847200 -0.01896700

H 3.93830100 -0.41591500 0.49094300

Sum of electronic and zero-point Energies= -340.800066

Sum of electronic and thermal Energies= -340.792353

Sum of electronic and thermal Enthalpies= -340.791408

Sum of electronic and thermal Free Energies= -340.833916

N2

N 0.00000000 0.00000000 0.54558200

N 0.00000000 0.00000000 -0.54558200

Sum of electronic and zero-point Energies= -109.565010

24

Sum of electronic and thermal Energies= -109.562650

Sum of electronic and thermal Enthalpies= -109.561706

Sum of electronic and thermal Free Energies= -109.583435