Artículo
On the accurate estimation of free energies using the jarzynski equality
Arrar, Mehrnoosh
; Boubeta, Fernando Martín
; Szretter Noste, María Eugenia; Sued, Raquel Mariela
; Boechi, Leonardo
; Rodriguez, Daniela
Fecha de publicación:
02/2019
Editorial:
John Wiley & Sons Inc
Revista:
Journal Of Computational Chemistry
ISSN:
0192-8651
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
The Jarzynski equality is one of the most widely celebrated and scrutinized nonequilibrium work theorems, relating free energy to the external work performed in nonequilibrium transitions. In practice, the required ensemble average of the Boltzmann weights of infinite nonequilibrium transitions is estimated as a finite sample average, resulting in the so-called Jarzynski estimator, (Formula presented.). Alternatively, the second-order approximation of the Jarzynski equality, though seldom invoked, is exact for Gaussian distributions and gives rise to the Fluctuation-Dissipation estimator (Formula presented.). Here we derive the parametric maximum-likelihood estimator (MLE) of the free energy (Formula presented.) considering unidirectional work distributions belonging to Gaussian or Gamma families, and compare this estimator to (Formula presented.). We further consider bidirectional work distributions belonging to the same families, and compare the corresponding bidirectional (Formula presented.) to the Bennett acceptance ratio ((Formula presented.)) estimator. We show that, for Gaussian unidirectional work distributions, (Formula presented.) is in fact the parametric MLE of the free energy, and as such, the most efficient estimator for this statistical family. We observe that (Formula presented.) and (Formula presented.) perform better than (Formula presented.) and (Formula presented.), for unidirectional and bidirectional distributions, respectively. These results illustrate that the characterization of the underlying work distribution permits an optimal use of the Jarzynski equality.
Palabras clave:
FREE ENERGY
,
JARZYNSKI
,
MAXIMUM-LIKELIHOOD
,
STEERED MOLECULAR DYNAMICS
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Articulos(INQUIMAE)
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos(OCA CIUDAD UNIVERSITARIA)
Articulos de OFICINA DE COORDINACION ADMINISTRATIVA CIUDAD UNIVERSITARIA
Articulos de OFICINA DE COORDINACION ADMINISTRATIVA CIUDAD UNIVERSITARIA
Citación
Arrar, Mehrnoosh; Boubeta, Fernando Martín; Szretter Noste, María Eugenia; Sued, Raquel Mariela; Boechi, Leonardo; et al.; On the accurate estimation of free energies using the jarzynski equality; John Wiley & Sons Inc; Journal Of Computational Chemistry; 40; 4; 2-2019; 688-696
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