Manuscript submitted to the Journal of the American Society for Mass Spectrometry, September 2011.

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1 The Early Life of a Peptide Cation-Radical. Ground and Excited-State Trajectories of Electron-Based Peptide Dissociations During the First 330 Femtoseconds Christopher L. Moss, Wenkel Liang, Xiaosong Li,* František Tureček* Department of Chemistry, Bagley Hall, Box , University of Washington, Seattle, WA Manuscript submitted to the Journal of the American Society for Mass Spectrometry, September Figures S1-S6, and Tables S1-S9 of optimized ion structures with total and zero-point energies. S1

2 Figure S1. Top panel (a) RRKM rate constants for C δ N ε (circles) and N ε H ε (triangles) dissociations in 3. Filled symbols: B3-PMP2/ G(2d,p) transition state energies; open symbols: M06-2X/ G(3df,2p) transition state energies. Bottom panel (b): Calculated ratios (log) of rate constants for loss of H and guanidine from 3 at the indicated levels of theory. S2

3 Figure S2. RRKM rate constant for N C α bond cleavage in 2 on the effective CCSD(T)/ G(3df,2p) potential energy surface of the ground doublet state. The vertical line indicates that ion internal energy after resonant electron transfer to (AR + 2H) 2+ from a Cs atom and isomerization to intermediate 2. S3

4 Figure S3. Time dependence of the H 3 N---C α bond length from Ehrenfest dynamics calculations of the SOMO state of (AR + 2H) + calculated with CAM-B3LYP/4-31G*. S4

5 Figure S4. Geometries at the indicated times from CAM-B3LYP/4-31G(d) Ehrenfest dynamics calculations of the LUMO state of (AR + 2H) +. θ is the N,C,N,N dihedral angle of the guanidine group. S5

6 Figure S5. Geometries at the indicated times from CAM-B3LYP/4-31G(d) Ehrenfest dynamics calculations of the LUMO+1 state of (AR + 2H) +. θ is the N,C,N,N dihedral angle of the guanidine group. S6

7 Figure S6. Time dependence of the guanidinium H ε N ε bond lengths from Ehrenfest dynamics calculations of the LUMO+2 state of (AR + 2H) + calculated with CAM-B3LYP/4-31G*. Black circles: H ε N ε bond; blue circles: H 11 N 1 bond; pink circles: H 12 N 1 bond; green circles: H 21 N 2 bond; turquoise circles: H 22 N 2 bond. S7

8 Table S1. B3LYP/6-31+G(d,p) optimized geometry of (AR + 2H) 2+ ion Rotational constants (GHZ): E(B3LYP)/6-31+G(d,p) = a.u. Zero point energy = kj mol -1 S8

9 Table S2. B3LYP/6-31+G(d,p) optimized geometry of (AR + 2H) 2+ cation-radical Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. Zero point energy = kj mol -1 E[PMP2/ G(3df,2p)] = a.u. E[CCSD(T)/6-31+G(d,p)] = a.u. E[CCSD(T)/ G(3df,2p)] = a.u. S9

10 Table S3. B3LYP/6-31+G(d,p) optimized geometry of (AR + 2H) 2+ cation-radical Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. Zero point energy = kj mol -1 E[PMP2/ G(3df,2p)] = a.u. E[CCSD(T)/6-31+G(d,p)] = a.u. E[CCSD(T)/ G(3df,2p)] = a.u. S10

11 Table S4. B3LYP/6-31+G(d,p) optimized geometry of (AR + 2H) 2+ cation-radical Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. Zero point energy = kj mol -1 E[PMP2/ G(3df,2p)] = a.u. E[CCSD(T)/6-31+G(d,p)] = a.u. E[CCSD(T)/ G(3df,2p)] = a.u. S11

12 Table S5. B3LYP/6-31+G(d,p) optimized geometry of TS(1 2) for side-chain rotation Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. Zero point energy = kj mol -1. S12

13 Table S6. B3LYP/6-31+G(d,p) optimized geometry of TS(N ε H ε ) for loss of H ε Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. Zero point energy = kj mol -1 E[PMP2/ G(3df,2p)] = a.u. E[CCSD(T)/6-31+G(d,p)] = a.u. E[CCSD(T)/ G(3df,2p)] = a.u. S13

14 Table S7. B3LYP/6-31+G(d,p) optimized geometry of TS(N C α ).for N C α bond cleavage Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. Zero point energy = kj mol -1 E[PMP2/ G(3df,2p)] = a.u. E[CCSD(T)/6-31+G(d,p)] = a.u. E[CCSD(T)/ G(3df,2p)] = a.u. S14

15 Table S8. B3LYP/6-31+G(d,p) optimized geometry of TS(C δ N ε ) for loss of guanidine Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. Zero point energy = kj mol -1 E[PMP2/ G(3df,2p)] = a.u. E[CCSD(T)/6-31+G(d,p)] = a.u. E[CCSD(T)/ G(3df,2p)] = a.u. S15

16 Table S9. B3LYP/6-31+G(d,p) optimized geometry of (AR + H) + by loss of H ε Rotational constants (GHZ): E[B3LYP/6-31+G(d,p)] = a.u. Zero point energy = kj mol -1 E[PMP2/ G(3df,2p)] = a.u. E[CCSD(T)/6-31+G(d,p)] = a.u. E[CCSD(T)/ G(3df,2p)] = a.u. S16

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