On the possible biological relevance of HSNO isomers: A computational investigation. Supplementary Information

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1 Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is The Royal Society of Chemistry 2014 On the possible biological relevance of HSNO isomers: A computational investigation Supplementary Information Supplementary Tables, Figures Cartesian Coordinates and Energies Lena V. Ivanova, Becka J. Anton and Qadir K. Timerghazin* Department of Chemistry, Marquette University,.PO. Box 1881, Milwaukee, Wisconsin qadir.timerghazin@marquette.edu * To whom correspondence should be addressed S1

2 Contents Supplementary Tables S1-S Supplementary Figures S1-S Cartesian Coordinates and Energies S2

3 Supplementary Tables S1-S8 Table S1 Calculated bond lengths, angles and dihedral angles for HSNO isomers and transition states TS1-TS6, see Figure 2 trans- HSNO r(s N)/Å r(n O)/Å S N O/ r(s- H)/Å N S- H/ S N- H- O/ E, Hartree AVDZ AVTZ AVQZ AV5Z CBS CBS TQ ΔQ ΔCV ΔSR CBS+CORR CBS TQ+CORR TZVPPD CBS- QB cis- HSNO r(s N)/Å r(n O)/Å S- N- O/ r(s H)/Å N- S- H/ S- N- H- O/ E, Hartree AVDZ AVTZ AVQZ AV5Z CBS CBS TQ ΔQ ΔCV ΔSR CBS+CORR CBS TQ+CORR S3

4 TZVPPD CBS- QB cis- HONS r(s N)/Å r(n O)/Å S N O/ r(o H)/Å N- O- H/ H- O- N- S/ E, Hartree AVDZ AVTZ AVQZ AV5Z CBS CBS TQ ΔQ ΔCV ΔSR CBS+CORR CBS TQ+CORR TZVPPD CBS- QB trans- HONS r(s N)/Å r(n O)/Å S N O/ r(o H)/Å N- O- H/ H- O- N- S/ E, Hartree AVDZ AVTZ AVQZ AV5Z CBS CBS TQ ΔQ ΔCV ΔSR S4

5 CBS+Q+CV+SR CBS TQ+Q+CV+SR TZVPPD CBS- QB SN(H)O r(s N)/Å r(n O)/Å r(s O)/Å r(n H)/Å S- N- O/ S- O- N- H/ E, Hartree AVDZ AVTZ AVQZ AV5Z CBS CBS TQ ΔQ ΔCV ΔSR CBS+CORR CBS TQ+CORR CASPT2/ AVDZ AVTZ AVQZ AV5Z CBS TZVPPD CBS- QB cycl- SONH r(s N)/Å r(n O)/Å r(s O)/Å r(n H)/Å S- N- O/ S- O- N- H/ E, Hartree AVDZ AVTZ AVQZ AV5Z S5

6 CBS CBS TQ ΔQ ΔCV ΔSR CBS+CORR CBS TQ+CORR CASPT2/ AVDZ AVTZ AVQZ AV5Z CBS TZVPPD CBS- QB TS1 r(s N)/Å r(n O)/Å S- N- O/ r(s H)/Å N- S- H/ O- N- S- H/ E, Hartree AVDZ AVTZ AVQZ AV5Z CBS CBS TQ ΔQ ΔCV ΔSR CBS+CORR CBS TQ+CORR S6

7 CBS- QB TS2 r(s N)/Å r(n O)/Å S- N- O/ r(o H)/Å N- O- H/ S- O- N- H/ E, Hartree AVDZ AVTZ AVQZ CBS TQ ΔQ ΔCV ΔSR CBS TQ+CORR TZVPPD CBS- QB TS3 r(s N)/Å r(n O)/Å S- N- O/ r(o H)/Å N- O- H/ S- N- O- H/ E, Hartree AVDZ AVTZ AVQZ CBS TQ ΔQ ΔCV ΔSR CBS TQ+CORR TZVPPD CBS- QB TS4 r(s N)/Å r(n O)/Å S- N- O/ r(n H)/Å S- N- H/ S- N- H- O/ E, Hartree S7

8 AVDZ AVTZ AVQZ CBS TQ ΔQ ΔCV ΔSR CBS TQ+CORR TZVPPD CBS- QB TS5 r(s N)/Å r(n O)/Å S- N- O/ r(n H)/Å S- N- H/ S- O- N- H/ E, Hartree AVDZ AVTZ AVQZ CBS TQ ΔQ ΔCV ΔSR CBS TQ+CORR CASPT2/ AVDZ AVTZ AVQZ AV5Z CBS TZVPPD U TZVPPD S8

9 CBS- QB TS6 r(s N)/Å r(n O)/Å S- N- O/ r(n H)/Å S- N- H/ S- N- O- H/ E, Hartree AVDZ AVTZ AVQZ CBS TQ ΔQ ΔCV ΔSR CBS TQ+CORR TZVPPD CBS- QB Table S2 Calculated T 1 and D 1 coupled cluster diagnostics for HSNO isomers and transition states TS1-TS6 at AVQZ, see Figure 2 structure T 1 D 1 cycl-sonh SN(H)O trans-hons cis-hons trans-hsno cis-hsno TS TS TS TS TS TS S9

10 Table S3 CASPT2 energy calculations for reaction SN(H)O cycl-sonh with CASPT2/AVXZ and single point MRCI+Q calculations with fixed reference function (kcal mol -1 ) E 5 E 5rxn CASPT2/ AVDZ AVTZ AVQZ AV5Z CBS ZPE CBS+ZPE MRCI+Q/ AVQZ//CASPT2/AVQZ AVQZ AVQZ+Q S10

11 Table S4 Calculated activation energies and energies for reactions represented on Figure 2 E 1 E 1rxn E 2 E 2rxn E 3 E 3rxn E 4 E 4rxn E 5 E 5rxn E 6 AVDZ AVTZ AVQZ AV5Z AV5Z // AVQZ CBS CBS TQ E 6rxn ΔQ ΔCV ΔSR ΔZPE CBS + CORR CORR CBS TQ+CORR CBS+CORR+ZPE CORR+ZPE CBS TQ+CORR+ZPE PBE0/def2-TZVPPD E elec E elec+zpe CBS-QB3 E elec E elec+zpe S11

12 Table S5 Calculated T 1 and D 1 coupled cluster diagnostics for TS8, hypervalent intermediate and TS9 for reaction cyclic structure with H 2S at AVTZ, see Figure 5 structure T 1 D 1 TS intermediate TS Table S6 Calculated energy difference of cis-hsno, cis-hons, trans-hons, SN(H)O and cycl-sonh with reference to trans-hsno ((kcal mol -1 ) cis-hsno cis-hons trans-hons SN(H)O cycl-sonh AVDZ AVTZ AVQZ AV5Z AV5Z // AVQZ CBS CBS TQ ΔQ ΔCV ΔSR ΔZPE CBS+CORR CORR CBS TQ+CORR CBS+CORR+ZPE CORR+ZPE CBS TQCORR+ZPE PBE0/def2-TZVPPD E elec E elec+zpe CBS-QB3 E elec E elec+zpe S12

13 Table S7 Calculated energy of water assisted reaction with CBS-QB3 (kcal/mol), see Figure 3 one water molecule E 2 E 2rxn E form (cishsno) Eelec ΔZPE Eelec+ΔZPE two water molecules Eelec ΔZPE Eelec+ΔZPE one water molecule E E 4 E form 4rxn (planar cyclo) Eelec ΔZPE Eelec+ΔZPE two water molecules Eelec ΔZPE Eelec+ΔZPE one water molecule E E 6 E form 6rxn (transhsno) Eelec ΔZPE Eelec+ΔZPE two water molecules Eelec ΔZPE Eelec+ΔZPE Table S8 Calculated energies for reaction, H 2S +cycl-sonh HSSH +HNO, without and with one water molecule with CBS-QB3 (kcal/mol (Sheme 1B). E E+ZPE E rxn E rxn+zpe 0 water water S13

14 Supplementary Figures S1-S2 Figure S1 Calculated bond length [r(s N)] vs AVxZ basis set size of cyclic isomer cycl-sonh. Figure S2 Geometries of transition state and product for water-assisted reaction H 2 S + cycl-sonh HSSH +HNO (Scheme 1B) calculated with CBS-QB3 S14

15 Cartesian Coordinates and Energies Cartezian coordinates and energy for molecules calculated AV5Z trans-hsno E = Hartree O N S H AV5Z cis-hsno E = Hartree O N S H AV5Z cis-hons E= Hartree S N O H AV5Z trans-hons E= Hartree S N O H AV5Z Y-isomer E= Hartree S N O H AV5Z cycl-sonh E= Hartree H N O S AV5Z TS1 E= Hartree S N O H AVQZ TS2 E= Hartree S N O S15

16 H AVQZ TS3 E= Hartree S N O H AVQZ TS4 E= Hartree S N O H AVQZ TS5 E= Hartree S N O H AVQZ TS6 E= Hartree S N O H CBS-QB3 TS2 E= Hartree S N O H CBS-QB3 TS2-1w E= Hartree O N S H O H H CBS-QB3 TS2-2w E= Hartree O S N O O H H H H S16

17 H CBS-QB3 TS4 E= Hartree S N O H CBS-QB3 TS4-1w E= Hartree S N O O H H H CBS-QB3 TS4-2w E= Hartree S N O H O H H H O H CBS-QB3 TS6 E= Hartree S N O H CBS-QB3 TS6-1w E= Hartree O S N O H H H CBS-QB3 TS6-2w E= Hartree O N S H O H H S17

18 H O H UPBE0/def2-TZVPPD TS7 E= Hartree S N O H S H H UPBE0/def2-TZVPPD TS7-1w E= Hartree S O S N O H H H H H UPBE0/def2-TZVPPD TS7-2w E= Hartree O H N S H S O H H H O H H AVTZ TS8 E= Hartree S S H H N O H AVTZ HSS(H)ONH intermediate E= Hartree S S O S18

19 N H H H AVTZ TS9 Energy= Hartree S S N O H H H S19

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