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An algorithm for the uniform sampling of iso‐energy surfaces and for the calculation of microcanonical averages
Author(s) -
Rapallo Arnaldo
Publication year - 2006
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20342
Subject(s) - thermostat , hessian matrix , sampling (signal processing) , molecular dynamics , potential energy , energy (signal processing) , statistical physics , algorithm , potential energy surface , computer science , mathematics , computational chemistry , physics , thermodynamics , classical mechanics , chemistry , quantum mechanics , statistics , molecule , filter (signal processing) , computer vision
In this article an algorithm is proposed to efficiently perform the uniform sampling of an iso‐energy surface corresponding to a fixed potential energy U of a molecular system, and for calculating averages of certain quantities over microstates having this energy (microcanonical averages). The developed sampling technique is based upon the combination of a recently proposed method for performing constant potential energy molecular dynamics simulations [Rapallo, A. J Chem Phys 2004, 121, 4033] with well‐established thermostatting techniques used in the framework of standard molecular dynamics simulations, such as the Andersen thermostat, and the Nose–Hoover chain thermostat. The proposed strategy leads to very accurate and drift‐free potential energy conservation during the whole sampling process, and, very important, specially when dealing with high‐dimensional or complicated potential functions, it does not require the calculation of the potential energy function hessian. The technique proved to be very reliable for sampling both low‐ and high‐dimensional surfaces. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 414–425, 2006