Intramolecular soft modes and intermolecular interactions in liquid acetone

Abstract

Resonant inelastic x-ray scattering spectra excited at the O1s −1 π * resonance of liquid acetone are presented. Scattering to the electronic ground state shows a resolved vibrational progression where the dominant contribution is due to the C-O stretching mode, thus demonstrating a unique sensitivity of the method to the local potential energy surface in complex molecular systems. For scattering to electronically excited states, soft vibrational modes and, to a smaller extent, intermolecular interactions give a broadening, which blurs the vibrational fine structure. It is predicted that environmental broadening is dominant in aqueous acetone.

Kohn-Sham density functional theory calculations of non-resonant and resonant x-ray emission spectroscopy

“…There is little variation in the computed line shapes between the three basis sets used. However, the spectra for the smallest basis set, 6-31G*, are shifted to higher energy by 0.5 eV and 1.5 eV for fluorobenzene and Cr(CO) 6 , respectively. The shift in energy arises from a combination of a lowering in the orbital energies of the valence orbitals and an increase in energy of the core orbital with the larger basis sets relative to the smaller 6-31G* basis set.…”

“…All of the molecules have a singlet ground state, except Cp 2 Cr which has a triplet ground state. Figure 2 illustrates the dependence of the Kohn-Sham DFT computed spectra for fluorobenzene (fluorine K-edge) and Cr(CO) 6 (chromium K-edge) on the quality of the basis set. There is little variation in the computed line shapes between the three basis sets used.…”

Theoretical simulations of oxygen K -edge resonant inelastic x-ray scattering of kaolinite

“…Information has been gained on potential energy surfaces, 1,2 quantum beats, 3 parity, 4 molecular dynamics 5,6 and the N 2 ionization threshold.…”

“…The investigated systems vary from simple homonuclear molecules, such as N 2 7 and O 2 , 2,3 to molecular liquids, such as acetone 5 and acetone-chloroform.…”

“…By studying the quasi-elastic RIXS process, where inhomogeneous electronic broadening is quenched and vibrational resolution can be achieved, we can probe the ground state potential energy surface, as shown in recent studies on gas phase, 1,2,8 on liquids, 1,5,6,9 and on solids.…”