Predissociation spectra of the ³⁵Cl⁻(H₂) complex and its isotopologue ³⁵Cl⁻(D₂)

Abstract

The predissociation spectra of the 35Cl-(H2) and 35Cl-(D2) complexes are determined within an accurate quantum approach and compared to those recently measured in an ionic trap at 8 K and...

Attachment of Hydrogen Molecules to Atomic Ions (Na+, Cl−): Examination of an Adiabatic Separation of the H2 Rotational Motion

“…The work is here extended with the application of the Ad‐PsAt model to both p/o H 2 isomers. Regarding chlorine clusters, recording of the vibrational spectra of both o H 2 Cl − and p H 2 Cl − dimers was achieved in recent experiments, [27] which confirmed theoretical predictions about strong differences in the spectral features of both spin isomers [25] . While we are not aware of experiments on larger clusters, some works have addressed their electronic structure, [28,29] showing the capacity of the anion for the attachment of hydrogen molecules.…”

“…One aspect of interest for hydrogen storage applications is the determination of the ion coordination number, i. e., the number of H 2 molecules that are directly attached to the ion, forming the first shell of the cluster. Since H 2 -ion binding energies are generally larger for oH 2 than for pH 2 , [24,25] it can be expected that more ortho molecules will be attached to the ion.…”

“…Regarding chlorine clusters, recording of the vibrational spectra of both oH 2 Cl À and pH 2 Cl À dimers was achieved in recent experiments, [27] which confirmed theoretical predictions about strong differences in the spectral features of both spin isomers. [25] While we are not aware of experiments on larger clusters, some works have addressed their electronic structure, [28,29] showing the capacity of the anion for the attachment of hydrogen molecules. In this work we present a new ab initio-based PES for H 2 -Cl À and report the properties of (H 2 ) n Cl À clusters as obtained within all the models previously mentioned.…”

Quantum study of the radiative association of Cl$$^-+\text {H}_2$$ and Cl$$^-+\text {D}_2$$

“…They also tried to measure the radiative association rate and concluded that it was too small to be measurable. In another related work a combined theoretical [10] and experimental determination of the pre-dissociation spectrum of the H 2 Cl complex was reported by [5]. A very good agreement between theory and experiment was obtained allowing to explain the strong ortho/para e↵ects in the vibrational spectrum of H 2 Cl .…”

“…It is based on the driven equation space fixed formalism (see [8] and references therein) which connects the bound and scattering wave functions through the light-matter interaction operator. The bound states energies and wave functions of the formed complex are first calculated using a variational approach as detailed in [10]. For given initial (J) and final (J') values of the total angular momentum, each of the matrix elements of the dipole moment operator between the complex bound states (↵, J 0 ) and the continuous scattering wave function describing the approach of Cl towards H 2 in a given ro-vibrational state (⌫, j) are then accumulated during the course of the propagation of the initial scattering wave function allowing to obtain the RA cross sections.…”