The influence of the detachment of electrons on the properties and the nature of interactions in X−H2O (X=Cl, Br) complexes

Abstract

Articles you may be interested inComparative density functional theory and post-Hartree-Fock (CCSD, CASSCF) studies on the electronic structure of halogen nitrites ClONO and BrONO using quantum chemical topology

Quantum Dynamics and Spectroscopy of Electron Photodetachment in Cl-···H2O and Cl-···D2O Complexes

“…34 The resulting potential has a global minimum of -4854 cm -1 (with respect to dissociation into Cland H 2 O fragments) at R ) 3.15 Å, corresponding to a planar geometry of the complex (φ ) 0°or φ ) 180°) with a nearly collinear Cl --H-O hydrogen bond (θ ) 44°). This structure (see Figure 2a) is in a quantitative agreement with previous calculations, [10][11][12]14,25 as well as experimental studies, 35,36 given the geometry constraint of the rigid water molecule mentioned above. The asymmetric, hydrogen-bonded optimal structure is preferred within a rather narrow region of R values around 3 Å.…”

“…Note that our DIM potential does not support another isomer such as the very shallow minimum close to the anionic geometry calculated recently . The corresponding structure at R = 3.55 Å is within our potential model a first-order saddle point with respect to the out-of-plane motion of the water molecule.…”

“…Note that our DIM potential does not support another isomer such as the very shallow minimum close to the anionic geometry calculated recently. 14 The corresponding structure at R ) 3.55 Å is within our potential model a first-order saddle point with respect to the out-of-plane motion of the water molecule. As will be discussed later, however, possible existence of such a shallow local minimum does not play any significant role in the dynamics following electron photodetachment.…”

“…Size-selected halide−water clusters, which represent a natural laboratory for studying the onset of ionic aqueous solvation, have been extensively studied by means of photoelectron spectroscopy, , as well as via ab initio quantum chemistry methods, − molecular dynamics (MD), − and quantum vibrational dynamics simulations. With the advent of ZEKE spectroscopy, the hitherto unexplored neutral complexes, created by electron photodetachment, became also accessible to experimental scrutiny.…”

Ab Initio Studies of the Microsolvation of Ions

“…26,27 Theoretical electron population analysis confirms the charge conservation on core ions in these complexes. [28][29][30] The positive charge is more delocalized compared to anionic clusters even through the central ion is still the distinctly charged center. 31 The ionization potential of CH 3 Ar n clusters is little changed as an effect of the consecutive argon coordination.…”