Recently Tobias and Broods introduced a method to compute by molecular dynamics with constraints the probability density P(≈r) = < δ(r - ≈r) &>; associated with rate values≈r of a spatial coordinate r. In this Letter we extend their approach to the case of a general reaction coordinate ξ(r), an arbitrary function of the configuration-space coordinates. The generalized version is shown to be the integral form of the free energy calculation in the constrained-reaction-coordinate ensemble where the mean force is computed as an average in a ξ-constrained ensemble. The two approaches are shown to be of equal computational efficiency for a very simple Lennard-Jones test case. © 1991.
Paci E., Ciccotti G., Ferrario M., Kapral R. (1991). Activation energies by molecular dynamics with constraints. CHEMICAL PHYSICS LETTERS, 176(6), 581-587 [10.1016/0009-2614(91)90259-C].
Activation energies by molecular dynamics with constraints
Paci E.;
1991
Abstract
Recently Tobias and Broods introduced a method to compute by molecular dynamics with constraints the probability density P(≈r) = < δ(r - ≈r) &>; associated with rate values≈r of a spatial coordinate r. In this Letter we extend their approach to the case of a general reaction coordinate ξ(r), an arbitrary function of the configuration-space coordinates. The generalized version is shown to be the integral form of the free energy calculation in the constrained-reaction-coordinate ensemble where the mean force is computed as an average in a ξ-constrained ensemble. The two approaches are shown to be of equal computational efficiency for a very simple Lennard-Jones test case. © 1991.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
