Nuclear–nuclear correlation function from non-Born–Oppenheimer calculations of diatomic rovibrational states with total angular momentum equal to two (N = 2). Charge asymmetry in HD. (18th May 2016)

• Record Type: Journal Article
• Authors: Jones, Keith; Formanek, Martin; Mazumder, Rahik; Kirnosov, Nikita; Adamowicz, Ludwik
• Is Part Of: Molecular physics. Volume 114:Number 10(2016)
• Page Start: 1634
• Page End: 1643
• Publication Date: 2016-05-18
• Subjects: Explicitly correlated Gaussian functions -- ab initio methods -- non-Born–Oppenheimer methods -- rovibrationally excited states; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2016.1142621
• Languages: English
• ISSNs: 0026-8976

Abstract

ABSTRACT: The HD molecule in rovibrational states where the total angular momentum quantum number is equal to two ( N = 2) is characterised with quantum mechanical calculations without assuming the Born–Oppenheimer (BO) approximation. Explicitly correlated all-particle Gaussian functions are used in the calculations. The convergence of the total non-BO energies of the considered states with the basis set size is analysed. The calculations of the averaged interparticle distances demonstrate the asymmetry of the electronic charge distribution. The algorithm to calculate the nuclear–nuclear correlation function for the N = 2 states is derived and implemented. Plots of this function for different rovibrational states provide a visual representation of the molecular structure. GRAPHICAL ABSTRACT: