We introduce a method to obtain one-dimensional collective variables for studying rarely occurring transitions between two metastable states separated by a high free energy barrier. No previous information, not even approximated, on the path followed during the transition is needed. The only requirement is to know the fluctuations of the system while in the two metastable states. With this information in hand, we build the collective variable using a modified version of Fisher's linear discriminant analysis. The usefulness of this approach is tested on the metadynamics simulation of two representative systems. The first is the freezing of silver iodide into the superionic α-phase, and the second is the study of a classical Diels-Alder reaction. The collective variable works very well in these two diverse cases.

Collective Variables from Local Fluctuations / Mendels, D.; Piccini, G.; Parrinello, M.. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 9:11(2018), pp. 2776-2781. [10.1021/acs.jpclett.8b00733]

Collective Variables from Local Fluctuations

Piccini G.;
2018

Abstract

We introduce a method to obtain one-dimensional collective variables for studying rarely occurring transitions between two metastable states separated by a high free energy barrier. No previous information, not even approximated, on the path followed during the transition is needed. The only requirement is to know the fluctuations of the system while in the two metastable states. With this information in hand, we build the collective variable using a modified version of Fisher's linear discriminant analysis. The usefulness of this approach is tested on the metadynamics simulation of two representative systems. The first is the freezing of silver iodide into the superionic α-phase, and the second is the study of a classical Diels-Alder reaction. The collective variable works very well in these two diverse cases.
2018
9
11
2776
2781
Collective Variables from Local Fluctuations / Mendels, D.; Piccini, G.; Parrinello, M.. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 9:11(2018), pp. 2776-2781. [10.1021/acs.jpclett.8b00733]
Mendels, D.; Piccini, G.; Parrinello, M.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/1330778
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