Valence photoelectron spectra of alkali bromides calculated within the propagator theory

Abstract

The valence ionization spectra covering the binding energy range 0–45 eV of alkali bromide XBr (X = Li, Na, K, Rb) vapors are studied within the framework of the propagator theory. Relativistic Algebraic Diagrammatic Construction calculations have been carried out in order to investigate photoionization processes and to describe molecular electronic structure. Theoretical results are compared with available experimental data.

Breakdown of ionic character of molecular alkali bromides in inner-valence photoionization

“…16 All calculations in Ref. 5 were performed using the relativistic ab initio program DIRAC10 17 and Relativistic Algebraic Diagrammatic Construction method RELADC. 7,18 More details about calculations can be found in Ref.…”

“…Karpenko et al 5 showed that third-order algebraic diagrammatic construction (ADC) 6,7 method is capable of reproducing valence and inner-valence PES of alkali bromide molecules. It was pointed out that theoretically calculated PES for KBr is in good agreement with available experimental data.…”

“…8 By using this method the binding energies and ionization strengths for 4p and 4s orbitals of Br − , 2p orbital of Na + , 3p and 3s orbitals of K + , and 4p and 4s orbitals of Rb + were calculated. 5 To the best of our knowledge, any experimental synchrotron radiation studies of the inner-valence region of LiBr, NaBr, and RbBr have not been reported yet. In this paper, experimental results have been analyzed by comparing them with theoretical predictions, 5 as well as with experimental inner-valence PES of Kr (Ref.…”

Behavior of relative state selective photoionization cross sections of RbBr molecules in the valence region

“…Benzaid et al [5] reported a com prehensive experim ental study o f the partial photoionization cross sections o f atom ic B r across the entire autoionization regim e extending from the first ionization threshold B r+ (3P 2) to the highest threshold B r+ (] So). T he autoionization decay patterns arising from the *oleksandr.karpenko@oulu.fi Recently, K arpenko et al [7,8] show ed that the third-order algebraic diagram m atic construction (AD C) m ethod [9,10] im plem ented in the DIRAC 10 program [11] is capable of reproducing valence and inner-valence photoelectron spectra …”

“…(Color online) (a) Experimental inner-valence photoelec tron spectra of RbBr measured with 45,75, and 90 eV photon energies, (b) Theoretical spectrum, taken from Ref [7],. presented with vertical red bars.…”