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Title: Emergence of pseudo-time during optimal Monte Carlo sampling and temporal aspects of symmetry breaking and restoration
We argue that one can associate a pseudo-time with sequences of configurations generated in the course of classical Monte Carlo simulations for a single-minimum bound state if the sampling is optimal. Hereby, the sampling rates can be, under special circumstances, calibrated against the relaxation rate and frequency of motion of an actual physical system. The latter possibility is linked to the optimal sampling regime being a universal crossover separating two distinct suboptimal sampling regimes analogous to the physical phenomena of diffusion and effusion, respectively. Bound states break symmetry; one may thus regard the pseudo-time as a quantity emerging together with the bound state. Conversely, when transport among distinct bound states takes place—thus restoring symmetry—a pseudo-time can no longer be defined. One can still quantify activation barriers if the latter barriers are smooth, but simulation becomes impractically slow and pertains to overdamped transport only. Specially designed Monte Carlo moves that bypass activation barriers—so as to accelerate sampling of the thermodynamics—amount to effusive transport and lead to severe under-sampling of transition-state configurations that separate distinct bound states while destroying the said universality. Implications of the present findings for simulations of glassy liquids are discussed.  more » « less
Award ID(s):
1956389
PAR ID:
10404328
Author(s) / Creator(s):
;
Date Published:
Journal Name:
The Journal of Chemical Physics
Volume:
158
Issue:
12
ISSN:
0021-9606
Page Range / eLocation ID:
124119
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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