Valence one-electron and shake-up ionization bands of carbon clusters. I. The Cn (n=3,5,7,9) chains

Abstract

The 1h (one-hole) and 2h-1p (two-hole; one-particle) shake-up bands in the valence ionization spectrum of small carbon chains (C3,C5,C7,C9) are investigated up to 40 eV, using the one-particle Green’s function approach. Calculations have been performed at the second- and third-orders of an algebraic diagrammatic construction (ADC) scheme based on partial renormalization series, which incorporate static and dynamic electronic correlation consistently through those orders. The results obtained indicate a major or complete breakdown of the orbital picture of ionization extending down into the outer-valence energies for the largest chains (12.4 eV for C9). Cumulenic carbon chains represent the only case reported so far where outer-valence ionization lines of π character can be affected by severe fragmentation in shake-up sets. The one-hole states associated with the terminal carbon lone pairs are also very strongly affected by electronic relaxation.

High resolution electron momentum spectroscopy of the valence orbitals of water

“…1 in Ref. [54] and references therein), these states can be regarded as deriving from the diffusion of a strongly localized and almost atomic-like ðO À1 2s Þ 2a À1 1 electron hole vacancy into the 1b 1 (O 2p lone pair) orbital, along with a single electronic excitation from the same lone pair orbital into a very diffuse unoccupied xa 1 orbital (Fig. 3).…”

“…The sets of Feynman-Dyson transition amplitudes ({X fi }) required to expand Dyson orbitals derive [12,63] from the 1h and 1p components of the associated eigenvectors (HX = XE, X X = 1). By virtue of its treatment of static and dynamic self-energies, through fourth-and thirdorder in correlation [54], respectively, the 1p-GF/ADC(3) approach predicts vertical one-electron ionization energies within accuracies of $0.2 eV [64,65]. In contrast with comparable MR-SDCI (multi-reference single and double CI) treatments, the 1p-GF/ADC(3) scheme is size-consistent [66] and applicable therefore to extremely large systems [67].…”

“…(2) is referred to as a Dyson orbital [5][6][7][8][9][10][11][12]. Dyson orbitals are straightforwardly obtained from CI [31] or Green's Function (GF) calculations [9][10][11]54]. …”

Green's function study of the one‐electron and shake‐up ionization spectra of unsaturated hydrocarbon cage compounds

“…To date, the most efficient 1p-GF method for accurately studying one-electron and shake-up ionization states in large molecular systems is the socalled third-order algebraic diagrammatic construction scheme [ADC (3)]. [41][42][43][44] The purpose of the present work is therefore to study, both at the OVGF and ADC(3) levels, the available photoelectron spectra of a few representative cage compounds ( Fig. 1), within the assumption of a vertical depiction of ionization.…”

Quasiparticle band structure of infinite hydrogen fluoride and hydrogen chloride chains

“…30,31 Particularly, they have been examined in series of oligomers of increasing length which model infinite chains. 32,33,34,35,36 Yet in this work, we focus on the quasiparticle (or main) states for which a one to one correspondence to Hartree-Fock one-particle states can be established. Like the one-particle states, they form a so-called quasiparticle band structure.…”