Absorpcija rentgenske svetlobe v hidridih elementov skupin 3p in 4p

• Main Author: Hauko, Robert
• Other Authors: Padežnik Gomilšek, Jana
• Format: Doctoral or Postdoctoral Thesis
• Language: Slovenian
• Published: R. Hauko 2017
• Subjects: rentgenski absorpcijski spektri; plinasti hidridi; spektri 3p na robu K; spektri 4p na robu K; izračuni DFT; večelektronske vzbuditve; spektri sovzbuditev; otresanje; X-ray absorption spectra; gaseous hydrides; 3p K-edge spectra; 4p K-edge spectra; DFT calculation; multi-electron photoexcitations; co-excitation spectra; shake-up; shake-off; info:eu-repo/classification/udc/539.1:543.428.3(043.3); Orca
• Online Access: https://dk.um.si/IzpisGradiva.php?id=65229; https://dk.um.si/Dokument.php?id=111245&dn=; http://www.cobiss.si/scripts/cobiss?command=DISPLAY&base=cobib&rid=23098376&fmt=11

V območju energij roba K smo izmerili fotoabsorpcijske spektre plinastih hidridov elementov skupine 3p (PH3, H2S, HCl). Analizo smo razširili na že prej izmerjene hidride skupine 4p (GeH4, AsH3, H2Se, HBr) ter na žlahtna plina Ar in Kr in spekter SiH4, ki ni v dosegu naših meritev. Oblike robov in ostre strukture tik nad robom zrcalijo eno- in večelektronske prehode na molekulske in modificirane atomske orbitale. V analizo pod-robnih struktur smo vključili tudi objavljene homologne spektre skupine 2p (CH4, NH3, H2O and HF), vključno z žlahtnim plinom Ne, ki imajo robove v področju trde ultravijolične svetlobe. Strukturo roba smo modelirali z linearno kombinacijo resonančnih komponent, ki opisujejo vzbuditve v posamezna vezana stanja in v kontinuum. Relativne energije in verjetnosti posameznih prehodov, ki smo jih izračunali s programsko kodo ORCA, se dobro ujemajo z izmerjenimi vrednostmi. Robovi homolognih spektrov težjih hidridov so si zelo podobni, v vseh simetrija molekule narekuje prehode na najnižje nezasedene orbitale. V zaporedju 2p prevlada močan učinek jedrskega potenciala. Prehodi na višje, kvaziatomske nivoje, so zelo podobni prehodom v prostem atomu. Pri analizi valenčnih sovzbuditev nad absorpcijskim robom smo s postopkom dekonvolucije kompenzirali povečano naravno širino struktur pri skupini 4p. Podobnost oblik ostrih struktur v analognih parih spektrov kaže na enak sklopitveni mehanizem zunanjih elektronskih konfiguracij v obeh zaporedjih spektrov. Pokazali smo, da lahko višjeenergijski del sovzbuditvenega spektra dobro modeliramo s sovzbuditvenima spektroma Ar oz. Kr. Celotni presek za enojno ionizacijo ob prehodu drugega elektrona v vezano stanje kaže v obeh skupinah rahlo upadanje v odvisnosti od naboja centralnega atoma, pri čemer prevladuje prehod valenčnega elektrona na kvaziatomske orbitale. To je v nasprotju z rezultati meritev pri globokih sovzbuditvah, kjer prevladujejo prehodi na molekulske orbitale. Naša spoznanja potrjujejo nekatere novejše meritve v emisijski spektroskopiji. Celotna analiza in dobro ujemanje parametrov, ki smo jih izračunali v dvostopenjskem računu, z izmerjenimi, kaže na to, da lahko tudi valenčne sovzbuditve v molekulah hidridov skupin 3p in 4p dovolj dobro opišemo s približkom nenadnega prehoda: vzbujanju notranjega elektrona sledi relaksacija molekule z otresanjem valenčnega elektrona v višja vezana ali prosta stanja. Photoabsorption spectra of gaseous hydrides of 3p elements (PH3, H2S, HCl) are measured in the energy region of photoexcitations pertaining to K edge. The analysis is extended to hydrides of 4p series (GeH4, AsH3, H2Se, HBr) from an earlier experiment, and to noble gases Ar and Kr as well as the published spectrum of SiH4, inaccessible to our measurement. Edge profiles and sharp features immediately above the edges reflect single- and multi-electron transitions into molecular and modified atomic orbitals. In the pre-edge analysis, the published data on the homologous 2p series (CH4, NH3, H2O and HF) with Ne in the XUV region are included in the comparison. The edge profiles are modelled with a linear combination of lorentzian components, describing excitations to individual bound states and to continuum. Transition energies and probabilities are also calculated in the non-relativistic molecular model of the ORCA code, in good agreement with the experiment. Edge profiles in the heavier homologues are closely similar, the symmetry of the molecule governs the transitions to the lowest unoccupied orbitals. In 2p series the effect of the strong nuclear potential prevails. Transitions to higher, atomic-like levels remain very much the same as in free atoms. For analysis of valence coexcitations in the post-edge region the deconvolution procedure is used to compensate the increased natural widths of spectral structures in the 4p group. The similarity of the shape of the sharp structures in analog pairs of spectra proves that the coupling mechanism of the outer electronic configurations is mostly the same. We have shown that high-energy part of coexcitation spectra in hydrides can be modelled satisfactorly with a linear combination of multiplied Ar or Kr coexcitation spectra. The total cross-section for a single-electron ionization and transition of the second electron to the bound state shows a slightly decrease with an increasing charge of the central atom in both series, the transition of valence electron to the quasi-atomic orbitals dominate. The latter is in contrast with the results of multi-electron excitations higher up above the edge with prevailing transitions to molecular orbitals. Our findings are confirmed by some recent results in emission spectroscopy. The analysis and good agreement of parameters obtained in a two-steps calculation with measured values indicate that a valence co-excitation in gaseus hydrides of 3p and 4p elements can be described in the sudden approximation: the excitation of core electron is followed by the molecule relaxation with shake-up and shake-off transition of the outer electron.