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1 Eletroni Supplementry Mteril (ESI) for RSC Advnes. This journl is The Royl Soiety of Chemistry 2015 Eletroni Supplementry Informtion (ESI) for: Novel physio-hemil mehnism of the mutgeni tutomeristion of the Wtson-Crik-like A G nd C T DNA se mispirs: quntum-hemil piture Ol h O. Brovrets & Dmytro M. Hovorun Deprtment of Moleulr nd Quntum Biophysis, Institute of Moleulr Biology nd Genetis, Ntionl Ademy of Sienes of Ukrine, 150 Akdemik Zolotnoho Str., Kyiv, Ukrine Deprtment of Moleulr Biotehnology nd Bioinformtis, Institute of High Tehnologies, Trs Shevhenko Ntionl University of Kyiv, 2-h Akdemik Hlushkov Ave., Kyiv, Ukrine Corresponding uthor. Emil: dhovorun@img.org.u Tle S1. Energeti hrteristis of the investigted DNA se mispirs nd TSs of their tutomeristion vi the sequentil DPT otined t the different levels of theory for the geometry lulted t the B3LYP/ G(d,p) level of theory. Level of theory Complex MP2/ G(2df,pd) MP2/ G(3df,2pd) MP2/-pVTZ MP2/-pVQZ G E G E G E G E A G(WC) A G* (w) A G* (w) A* G (w) TS A+ G- A G(WC) A G* (w) A* G (w) TS A+ G- A G(WC) A* G (w) TS A- G+ A G(WC) A G* (w) TS A- G+ A G(WC) A* G (w) C T(WC) C* T (w) C* T (w) C T* O2 (w) TS C* T (w) C T*O2 (w) C* T*(WC) TS C T(WC) C* T*(WC) C T* (w) C T* (w) TS C+ T- C* T*(WC) C* T (w) TS C+ T- C* T*(WC) C T* (w) TS C- T+ C T(WC) C* T (w) TS C- T+ C T(WC) C T* (w) The reltive Gis free energy of the investigted omplexes ( G A G(WC)/C T(WC) =0.00; T= K), kl mol -1 The reltive eletroni energy of the investigted omplexes ( E A G(WC)/C T(WC) =0.00), kl mol -1 S1

2 Tle S2. Interse intertion energies (in kl mol -1 ) for the investigted DNA se mispirs nd TSs of their onversions vi the sequentil DPT otined t the MP2/ G(3df,2pd)//B3LYP/ G(d,p) level of theory. Complex -ΔE int ΣE HB ΣE HB / ΔE int, % -ΔG int A G(WC) A G* (w) A G* (w) A* G (w) A* G (w) TS A- G+ A G(WC) A G* (w) TS A+ G- A G(WC) A G* (w) TS A+ G- A G(WC) A* G (w) TS A- G+ A G(WC) A* G (w) C T(WC) C* T (w) C* T (w) C T* O2 (w) C* T*(WC) C T* (w) C T* (w) TS C+ T- C* T*(WC) C* T (w) TS C+ T- C* T*(WC) C T* (w) TS C- T+ C T(WC) C* T (w) TS C- T+ C T(WC) C T* (w) The BSSE-orreted eletroni intertion energy The totl energy of the intermoleulr H-onds (see Tle 1) The BSSE-orreted Gis free energy of intertion (T= K), Dt re tken from the works [Brovrets O.O., Zhurkivsky R.O., Hovorun D.M. (2014). Is the DPT tutomeristion of the long A G Wtson-Crik DNA se mispir soure of the denine nd gunine mutgeni tutomers? A QM nd QTAIM response to the iologilly importnt question. Journl of Computtionl Chemistry, 35, ] nd [Brovrets, O.O., & Hovorun, D.M. (2013). Atomisti understnding of the C T mismthed DNA se pir tutomeriztion vi the DPT: QM nd QTAIM omputtionl pprohes. Journl of Computtionl Chemistry, 34, ], respetively. S2

3 () () Fig. S1. Profiles of the R(H 9 -H 9' ) distnes etween the H 9 nd H 9' glyosidi hydrogens nd the α 1 ( N9H 9 (G)H 9' (A)) or α 2 ( N9H 9' (A)H 9 (G)) glyosidi ngles of the G nd A DNA ses, respetively, long the IRC of the () A G(WC) A G* (w) nd () A G(WC) A* G (w) tutomeristions vi the sequentil DPT otined t the B3LYP/ G(d,p) level of theory (see Figs. 1 nd 2). S3

4 TS A G(WC) (ν i =-324.6i m -1 ) TS TS A+ G- A G(WC) A G* (w) (ν i =-417.3i m -1 ) TS TS A+ G- A G(WC) A* G (w) (ν i =-77.5i m -1 ) () () () TS A* G (w) TS C T* (w) (ν i =-184.7i m -1 ) (ν i =-16.3i m -1 ) (d) (e) Fig. S2. Trnsition sttes of the onformtionl interonversions of the mirror-symmetri enntiomers of the () A G(WC), () TS A+ G- A G(WC) A G* (w), () TS A+ G- A G(WC) A* G (w), (d) A* G (w) nd (e) TS C T* (w) iologilly importnt omplexes. Dotted lines indite AH B H-onds (their lengths re presented in ngstroms). Cron toms re in light-lue, nitrogen in drk-lue, hydrogen in grey nd oxygen in red. ν i imginry frequeny. Tle S3. Energeti, virtionl, kineti nd geometri hrteristis of the onformtionl interonversions of the mirror-symmetri enntiomers of the iologilly importnt DNA se mispirs nd TSs of their tutomeristion vi the sequentil DPT lulted t the MP2/-pVQZ//B3LYP/ G(d,p) level of theory. Trnsition stte of the G TS E TS τ 99.9% ν d i β e interonversion TS A G(WC) i C6N1(G)N1C6(A)=±21.9 TS A+ G- TS A G(WC) A G* (w) i C6N1(G)N1C6(A)=±39.9 TS A+ G- TS A G(WC) A* G (w) i C6N1(G)N1C6(A)=±7.1 TS A* G (w) i C6N1(G)N1C6(A)=±93.5 TS C T* (w) i C5N3(T)C2N3(C)=±34.3 The Gis free energy rrier of the onformtionl interonversion under norml onditions, kl mol -1 The eletroni energy rrier of the onformtionl interonversion, kl mol -1 The time neessry to reh 99.9% of the equilirium onentrtion etween the mirror-symmetri enntiomers, s d Imginry frequeny in the trnsition stte of the onformtionl interonversion, m -1 S4

5 e Dihedrl ngle tht hrterize the non-plnrity of the omplex, degree; signs ± orrespond to the mirror-symmetri enntiomers Fig. S3. Profile of the reltive eletroni energy ΔE of the onformtionl interonversion of the mirror-symmetri enntiomers of the A* G (w) se mispir vi the rottion of the NH 2 mino group of the G se long the IRC otined t the B3LYP/ G(d,p) level of theory. S5

6 C* T (w) TS C* T (w) C T*O2 (w) C T* O2 (w) (ν i =-807.1i m -1 ) Fig. S4. Strutures orresponding to the sttionry points on the retion pthwy of the C* T (w) C T* O2 (w) onversion vi the sequentil DPT otined t the B3LYP/ G(d,p) level of theory. Dotted lines indite AH B H-onds nd ontinuous lines loosened A-H-B ovlent ridges (their lengths re presented in ngstroms). Cron toms re in light-lue, nitrogen in drk-lue, hydrogen in grey nd oxygen in red. ν i imginry frequeny. Tle S4. Energeti nd kineti hrteristis of the C* T (w) C T* O2 (w) tutomeristion vi the sequentil DPT otined t the different levels of theory for the geometry lulted t the B3LYP/ G(d,p) level of theory. Level of theory G E G TS E TS d G e E f τ 99.9% g MP2/ G(2df,pd) MP2/ G(3df,2pd) MP2/-pVTZ MP2/-pVQZ The Gis free energy of the produt reltively the retnt of the tutomeristion retion ( G C* T (w) =0.00 kl mol -1 ; T= K), kl mol -1 The eletroni energy of the produt reltively the retnt of the tutomeristion retion ( E C* T (w) =0.00 kl mol -1 ), kl mol -1 The Gis free energy rrier for the forwrd retion of tutomeristion, kl mol -1 d The eletroni energy rrier for the forwrd retion of tutomeristion, kl mol -1 e The Gis free energy rrier for the reverse retion of tutomeristion, kl mol -1 f The eletroni energy rrier for the reverse retion of tutomeristion, kl mol -1 g The time neessry to reh 99.9%of the equilirium onentrtion etween the retnt nd the produt of the tutomeristion retion, s See lso summry Tle S1 for the Gis nd eletroni energies of the DNA mispirs nd TSs reltively the glol minimum the short Wtson-Crik-like C T(WC) DNA se mispir. S6

7 Fig. S5. Profile of the reltive eletroni energy ΔE of the DNA se mispir long the IRC of the C* T (w) C T* O2 (w) tutomeristions vi the sequentil DPT otined t the B3LYP/ G(d,p) level of theory. S7

8 () () Fig. S6. Profiles of the R(H 1 -H 1' ) distnes etween the H 1 nd H 1' glyosidi hydrogens nd the α 1 ( N1H 1 (C)H 1' (T)) or α 2 ( N1H 1' (T)H 1 (C)) glyosidi ngles of the C nd T DNA ses, respetively, long the IRC of the () C T(WC) C* T (w) nd () C T(WC) C T* (w) tutomeristions vi the sequentil DPT otined t the B3LYP/ G(d,p) level of theory (see Figs. 4 nd 5). S8