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Dynamic treatment of vibrational energy relaxation in a heterogeneous and fluctuating environment
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10.1063/1.2985606
/content/aip/journal/jcp/129/13/10.1063/1.2985606
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/13/10.1063/1.2985606

Figures

Image of FIG. 1.
FIG. 1.

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).

Image of FIG. 2.
FIG. 2.

MD snapshot of NMA and its 16 nearest water molecules.

Image of FIG. 3.
FIG. 3.

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 .

Image of FIG. 4.
FIG. 4.

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) .

Image of FIG. 5.
FIG. 5.

Same as in Fig. 4, but for fully deuterated NMA. The VER times are (a) , (b) , (c) , and (d) .

Image of FIG. 6.
FIG. 6.

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.

Image of FIG. 7.
FIG. 7.

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.

Tables

Generic image for table
Table I.

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.

Generic image for table
Table II.

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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/content/aip/journal/jcp/129/13/10.1063/1.2985606
2008-10-06
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Dynamic treatment of vibrational energy relaxation in a heterogeneous and fluctuating environment
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/13/10.1063/1.2985606
10.1063/1.2985606
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