Molecular Dynamics of Artificially Pair-Decoupled Systems: An Accurate Tool for Investigating the Importance of Intramolecular Couplings.

ABSTRACT: We propose a numerical technique to accurately simulate the vibrations of organic molecules in the gas phase, when pairs of atoms (or, in general, groups of degrees of freedom) are artificially decoupled, so that their motion is instantaneously decorrelated. The numerical technique we have developed is a symplectic integration algorithm that never requires computation of the force but requires estimates of the Hessian matrix. The theory we present to support our technique postulates a pair-decoupling Hamiltonian function, which parametrically depends on a decoupling coefficient α ∈ [0, 1]. The closer α is to 0, the more decoupled the selected atoms. We test the correctness of our numerical method on small molecular systems, and we apply it to study the vibrational spectroscopic features of

SUBMITTER: Gandolfi M 

PROVIDER: S-EPMC10536992 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature