Dataset Information

Eddy current and coupled landscapes for nonadiabatic and nonequilibrium complex system dynamics.

ABSTRACT: Physical and biological systems are often involved with coupled processes of different time scales. In the system with electronic and atomic motions, for example, the interplay between the atomic motion along the same energy landscape and the electronic hopping between different landscapes is critical: the system behavior largely depends on whether the intralandscape motion is slower (adiabatic) or faster (nonadiabatic) than the interlandscape hopping. For general nonequilibrium dynamics where Hamiltonian or energy function is unknown a priori, the challenge is how to extend the concepts of the intra- and interlandscape dynamics. In this paper we establish a theoretical framework for describing global nonequilibrium and nonadiabatic complex system dynamics by transforming the coupled landscapes into a single landscape but with additional dimensions. On this single landscape, dynamics is driven by gradient of the potential landscape, which is closely related to the steady-state probability distribution of the enlarged dimensions, and the probability flux, which has a curl nature. Through an example of a self-regulating gene circuit, we show that the curl flux has dramatic effects on gene regulatory dynamics. The curl flux and landscape framework developed here are easy to visualize and can be used to guide further investigation of physical and biological nonequilibrium systems.

SUBMITTER: Zhang K

PROVIDER: S-EPMC3773781 | biostudies-literature | 2013 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Eddy current and coupled landscapes for nonadiabatic and nonequilibrium complex system dynamics.

Zhang Kun K Sasai Masaki M Wang Jin J

Proceedings of the National Academy of Sciences of the United States of America 20130826 37

Physical and biological systems are often involved with coupled processes of different time scales. In the system with electronic and atomic motions, for example, the interplay between the atomic motion along the same energy landscape and the electronic hopping between different landscapes is critical: the system behavior largely depends on whether the intralandscape motion is slower (adiabatic) or faster (nonadiabatic) than the interlandscape hopping. For general nonequilibrium dynamics where H ...[more]

PMID: 23980160

Similar Datasets

Project description:The coupling between electrons and protons and the long-range transport of protons play important roles throughout biology. Biomimetic systems derived from benzimidazole-phenol (BIP) constructs have been designed to undergo proton-coupled electron transfer (PCET) upon electrochemical or photochemical oxidation. Moreover, these systems can transport protons along hydrogen-bonded networks or proton wires through multiproton PCET. Herein, the nonequilibrium dynamics of both single and double proton transfer in BIP molecules initiated by oxidation are investigated with first-principles molecular dynamics simulations. Although these processes are concerted in that no thermodynamically stable intermediate is observed, the simulations predict that they are predominantly asynchronous on the ultrafast time scale. For both systems, the first proton transfer typically occurs ∼100 fs after electron transfer. For the double proton transfer system, typically the second proton transfer occurs hundreds of femtoseconds after the initial proton transfer. A machine learning algorithm was used to identify the key molecular vibrational modes essential for proton transfer: a slow, in-plane bending mode that dominates the overall inner-sphere reorganization, the proton donor-acceptor motion that leads to vibrational coherence, and the faster donor-hydrogen stretching mode. The asynchronous double proton transfer mechanism can be understood in terms of a significant mode corresponding to the two anticorrelated proton donor-acceptor motions, typically decreasing only one donor-acceptor distance at a time. Although these PCET processes appear concerted on the time scale of typical electrochemical experiments, attaching these BIP constructs to photosensitizers may enable the detection of the asynchronicity of the electron and multiple proton transfers with ultrafast two-dimensional spectroscopy. Understanding the fundamental PCET mechanisms at this level will guide the design of PCET systems for catalysis and energy conversion processes.

Dataset Information

Eddy current and coupled landscapes for nonadiabatic and nonequilibrium complex system dynamics.

Publications

Eddy current and coupled landscapes for nonadiabatic and nonequilibrium complex system dynamics.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets