title: Sampling Molecular Conformers in Solution with Quantum Mechanical Accuracy at a Nearly Molecular-Mechanics Cost.
abstract: We introduce a method to evaluate the relative populations of different conformers of molecular species in solution, aiming at quantum mechanical accuracy, while keeping the computational cost at a nearly molecular-mechanics level. This goal is achieved by combining long classical molecular-dynamics simulations to sample the free-energy landscape of the system, advanced clustering techniques to identify the most relevant conformers, and thermodynamic perturbation theory to correct the resulting populations, using quantum-mechanical energies from density functional theory. A quantitative criterion for assessing the accuracy thus achieved is proposed. The resulting methodology is demonstrated in the specific case of cyanin (cyanidin-3-glucoside) in water solution.
authors: SISSA - Scuola Internazionale Superiore di Studi Avanzati , via Bonomea 265, 34136 Trieste, Italy.
authors: Marta
authors: M
authors: Rosa
authors: SISSA - Scuola Internazionale Superiore di Studi Avanzati , via Bonomea 265, 34136 Trieste, Italy.
authors: Marco
authors: M
authors: Micciarelli
authors: SISSA - Scuola Internazionale Superiore di Studi Avanzati , via Bonomea 265, 34136 Trieste, Italy.
authors: Alessandro
authors: A
authors: Laio
authors: SISSA - Scuola Internazionale Superiore di Studi Avanzati , via Bonomea 265, 34136 Trieste, Italy.
authors: Stefano
authors: S
authors: Baroni
mesh_terms: D000872:Anthocyanins / Q000737:chemistry*; D005960:Glucosides / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D000872:Anthocyanins; D005960:Glucosides; C462279:cyanidin-3-O-beta-glucopyranoside; D014867:Water