Figure 1

Fragmentation yields of protonated TrpGly dipeptide ($[\mathrm{TrpGlyH}{]}^{+}$), bare $\mathrm{Ag}_3{}^{+}$ cluster and the $[\mathrm{TrpGly}·{\mathrm{Ag}}_3{]}^{+}$ complex as a function of wavelength. Solid lines are smoothed curves of the experimental data. $[\mathrm{TrpGlyH}{]}^{+}$ was obtained using the same electrolyte solution as for $[\mathrm{TrpGly}·{\mathrm{Ag}}_3{]}^{+}$. $\mathrm{Ag}_3{}^{+}$ was produced by fragmentation of $[\mathrm{TrpGly}·{\mathrm{Ag}}_3{]}^{+}$.Reuse & Permissions

Figure 2

(a) Theoretically simulated thermally broadened absorption spectrum of $[\mathrm{TrpGly}·{\mathrm{Ag}}_3{]}^{+}$ at $T=300\mathrm{K}$ compared with experimental photofragmentation spectrum (red curve). The black and green sticks correspond to the statistical ensembles of spectra around the most stable isomers I and II, respectively. (b) Thermal ensemble of structures at $T=300\mathrm{K}$ obtained from constant temperature MD simulations. (c) The analysis of the leading excitations between occupied and virtual Kohn-Sham orbitals participating in the intense transition at 288 nm. HOMO and LUMO label the highest occupied and the lowest unoccupied Kohn-Sham orbitals. (d) Electron density difference between electronically excited state and the ground state at 288 nm corresponding to the dominant optically allowed transition.Reuse & Permissions

Figure 3

(a) Experimental branching ratios for different fragmentation channels of $[\mathrm{TrpGly}·{\mathrm{Ag}}_3{]}^{+}$ as a function of the wavelength. (b) Snapshots of the MD in the electronic excited state located around 288 nm from selected trajectory at $T=300\mathrm{K}$ illustrating fragmentation of ${\mathrm{Ag}}_2$ dimer (upper part) and Ag atom (lower part).Reuse & Permissions

Figure 4

(a) and (b) Two-dimensional potential energy surface for TrpGly as a function of the dihedral angles corresponding to the rotation of the ${\mathrm{C}}_{\alpha }^{Gly}-\mathrm{N}$ and the ${\mathrm{C}}_{\alpha }^{Trp}-\mathrm{C}$ bonds neighboring the peptide bond (${\Phi }^{*}$, ${\Psi }^{*}$). The black curves in (a) and (b) represent the projection of the MD trajectories for TrpGly and $[\mathrm{TrpGly}·{\mathrm{Ag}}_3{]}^{+}$, respectively. (c) and (d) Ramachandran plot for $\mathrm{Trp}(\mathrm{Ala}{)}_2$ together with the constant temperature MD trajectories for $\mathrm{Trp}(\mathrm{Ala}{)}_2$ and $[\mathrm{Trp}(\mathrm{Ala}{)}_2·{\mathrm{Ag}}_3{]}^{+}$ (black curves).Reuse & Permissions