Mean VER probability as obtained for NMA in . Compared is the outcome of direct averaging [Eqs. (15) and (14), red full line], cumulant approximation [Eq. (16), green dashed line] and the naive ansatz (blue dotted line).
MD snapshot of NMA and its 16 nearest water molecules.
Time evolution of the vibrational dynamics of NMA in , as obtained from instantaneous normal mode analysis of a single trajectory with (right) and without (left) partial energy minimization. Shown are (upper panels) the normal mode frequencies of selected vibrational modes, (middle panels) the frequency mismatch for several resonant bath mode combinations, and (lower panels) the corresponding third-order anharmonic couplings .
Amide I mode relaxation probability of NMA, as obtained from an instantaneous normal mode analysis with (right) and without (left) partial energy minimization. Shown are results from (upper panels) the inhomogeneous averaging approximation and (lower panel) dynamics averaging. The VER times according to Eq. (24) are (a) , (b) , (c) , and (d) .
Same as in Fig. 4, but for fully deuterated NMA. The VER times are (a) , (b) , (c) , and (d) .
Influence of the solvent on the amide I mode relaxation in NMA. Including 16 (a), 32 (b), or all (c) water molecules in the calculations, the resulting overall VER appears to be quite similar. In the case of isolated NMA [thick dashed line in (a)], however, the relaxation probability follows the solution-phase decay only up to . Note that in the absence of solvent molecules, all trajectories coincide.
Comparison of calculated (red full lines) and experimental (green dashed lines) results for the VER of the amide I mode in NMA. Shown are data for (a) singly and (b) fully deuterated NMAs.
Dominant energy flow pathways of singly deuterated NMA (upper panel) and fully deuterated NMA (lower panel). The VER from of the initially excited amide I mode to the vibrational modes and is characterized by their path-specific relaxation times (in ps), time-averaged Fermi resonance parameter , frequency mismatch (in ), and third-order coupling element (in ), respectively.
Characterization of the normal modes that mainly participate in the VER of singly deuterated NMA (upper panel) and fully deuterated NMA (lower panel). Shown are the vibrational frequency and various projections on atomic coordinates [see Eq. (26)]. Mode 141 is the amide I mode.
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