Theory and ab initio calculations of 2p photoabsorption spectra: The lowest Rydberg resonances in HCl

Abstract

Articles you may be interested inTwo-dimensional ( 2 + n ) resonance enhanced multiphoton ionization of HCl: Photorupture channels via the F Δ 2 1 Rydberg state and ab initio spectra Extensive ab initio study of the valence and low-lying Rydberg states of BBr including spin-orbit coupling Ab initio calculation of ( 2 + 1 ) resonance enhanced multiphoton ionization spectra and lifetimes of the ( D , 3 ) Σ − 2 states of OH and OD J. Chem. Phys. 123, 074310 (2005); 10.1063/1.1997133Ab initio configuration interaction study of the predissociation of the (4s), (4pσ) 1,3 Π, and (4pπ) 3 Σ + Rydberg states of HCl and DClWe present a theory for 2p core excitation spectra of linear molecules that explicitly includes the spin-orbit splitting of the 2p core orbitals as well as all nonrelativistic effects. This is applied to the absorption spectrum of HCl at the 2p→6*, 4s, 4p, 3d, and 5s resonance energies. All input data for the spectrum are obtained from ab initio calculations. These are ͑i͒ the nonrelativistic energies and transition probabilities of the contributing states, ͑ii͒ the spin-orbit coupling parameter, and ͑iii͒ the total Auger transition rates of the core excited states. The prior theoretical finding that the total Auger decay rate depends substantially on the core hole orientation is supported by a comparison of the theoretical and experimental absorption spectra. Furthermore, the preferred orientation of the core excited HCl molecule with respect to the molecular bond axis is discussed. General considerations about intensity ratios between corresponding states with 2p 3/2 and 2p 1/2 holes are given on the basis of the theoretical framework.

The Cl(2p) photoelectron spectra of the HCl and DCl molecules: the effects of the molecular field

“…The MF splitting in p and d core hole states has been extensively studied in recent years by several authors: see, e.g., [1][2][3][4][5][6][7][8].Recently, Gel'mukhanov et al [3] and Fink et al [9] predicted that the non-spherical electron distribution of a molecule causes an anisotropy on the Auger decay probabilities of the 2p core hole states of H 2 S and HCl. This finding was supported in a recent comparison [10] of the computed and experimental 2p photoabsorption profiles of HCl. The aim of the present study is to confirm the effect of the MF on the Cl(2p) total decay rates in HCl.…”

A new method to derive electronegativity from resonant inelastic x-ray scattering

“…We estimate our calculated values of 2p z (%) to be uncertain by at most ±3%, as can be seen by comparison of experiment and theory (e.g., for HCl and CF 3 Cl, the experimental 2p z populations are 54% and 52%, respectively, while they are 52% and 51% from theory; see also Ref. 44, where 2p z = 52% for HCl). As a result, electronegativities determined with the new scale could be uncertain by as much as ±0.4.…”

Simulation of Auger decay dynamics in the hard X-ray regime: HCl as a showcase

“…10 as black dots and red line, respectively. Interestingly, this final state can only be accessed through shake processes but not by a spectator decay via the 1s −1 3dσ state since such excitations are not present in the absorption spectrum; this excitation is expected to be located approximately 1.5 eV above the 1s −1 4sσ state 45 , but no features are visible in this region of the spectrum. This observation may be explained as follows: in the core-excited state the 3dσ Rydberg orbital is still rather atomic-like so that the dipole selection rules for atoms explain the absence of this excitation in the absorption spectrum.…”