Dissociation of chloromethanes upon resonant σ∗ excitation studied by x-ray scattering (original) (raw)
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Physical Review A, 2012
Polarization-dependent resonant inelastic x-ray scattering (RIXS) has been shown to be a probe of molecularfield effects on the electronic structure of isolated molecules. In this experimental analysis we explain the linear dichroism observed in Cl 2p polarized RIXS following Cl 1s excitation of a series of chlorofluoromethanes (CF 3 Cl, CF 2 Cl 2 , CFCl 3 , and CCl 4 ) as due to molecular-field effects, including singlet-triplet exchange. We present an approach to extract directly the 2p inner-shell electronic state populations from the experimental measurements. Using the angular properties of the measured KV emission we also are able to determine the value of the polarization anisotropy parameter β p for each resolved component of the KV emission spectra.
Resonant inelastic x-ray scattering of methyl chloride at the chlorine K edge
The Journal of Chemical Physics, 2012
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Dissociative electron attachment and vibrational excitation of the chlorine molecule
Physical Review A, 2006
We present a study of dissociative electron attachment and vibrational excitation processes in electron collisions with the CF 3 Cl molecule. The calculations are based on the two-dimensional nuclear dynamics including the C-Cl symmetric stretch coordinate and the CF 3 symmetric deformation (umbrella) coordinate. The complex potential energy surfaces are calculated using the ab initio R-matrix method. The results for dissociative attachment and vibrational excitation of the umbrella mode agree quite well with experiment while the cross section for excitation of the C-Cl symmetric stretch vibrations is about a factor of three low as compared to experimental data. 1 12 Dissociative electron attachment (DEA) to polyatomic molecules typically involves mul-13 tidimensional nuclear dynamics. However, because of big computational work necessary 14 to obtain multidimensional complex (i.e., including both real and imaginary parts) energy 15 surfaces, most of theoretical DEA calculations were performed in one-dimensional approx-16 imation. In these calculations it is usually assumed that the DEA process involves one 17 reaction (dissociating) coordinate, roughly corresponding to one of the normal modes of the 18 target molecule. This approximation is sometimes too crude, and sometimes completely un-19 justified. Therefore, a lot of effort was devoted recently to calculations of multidimensional 20 DEA dynamics [1-6]. These calculations address two important problems in the physics of 21 DEA processes. First, we want to know which dissociation channels are the most important 22
Linear dichroism in molecular resonant inelastic x-ray scattering
Journal of Physics: Conference Series, 2009
Polarization-dependent resonant inelastic x-ray scattering (RIXS) is shown to be a new probe of molecular-field effects on the electronic structure of isolated molecules. A combined experimental and theoretical analysis explains the linear dichroism observed in Cl 2p RIXS following Cl 1s excitation in HCl and CF 3 Cl as due to molecular-field effects, including singlet-triplet exchange, indicating polarized-RIXS provides a direct probe of spin-orbit-state populations applicable to any molecule.
Linear Dichroism in Resonant Inelastic X-Ray Scattering to Molecular Spin-Orbit States
Polarization-dependent resonant inelastic x-ray scattering (RIXS) is shown to be a new probe of molecular-field effects on the electronic structure of isolated molecules. A combined experimental and theoretical analysis explains the linear dichroism observed in Cl 2p RIXS following Cl 1s excitation in HCl and CF 3 Cl as due to molecular-field effects, including singlet-triplet exchange, indicating polarized-RIXS provides a direct probe of spin-orbit-state populations applicable to any molecule.
Resonant Inelastic Scattering Spectra of Free Molecules with Vibrational Resolution
Inelastic x-ray scattering spectra excited at the 1s À1 Ã resonance of gas phase O 2 have been recorded with an overall energy resolution that allows for well-resolved vibrational progressions. The nuclear wave packet dynamics in the intermediate state is reflected in vibrational excitations of the electronic ground state, and by fine-tuning the excitation energy the dissociation dynamics in the predissociative B 0 3 Å g final state is controlled.
Journal of Chemical Theory and Computation, 2018
A coupled cluster protocol rooted in damped response theory is presented for computing Resonant Inelastic X-Ray Scattering spectra of molecules in gas-phase. Working equations are reported for both linear (i.e., equation-of-motion) and non-linear parametrizations of the coupled-cluster wavefunction response. A simple scheme to compute non-resonant X-ray emission spectra is also proposed. Illustrative results are presented for water.
The Journal of Chemical Physics, 2008
Core excitation triggers nuclear dynamics on the femtosecond time scale. A multiparametric electron/ion coincidence approach has been used to disentangle complex decay processes occurring at short ͑molecular͒ or long ͑atomic͒ time scales. Methyl chloride has been excited by scanning along the dissociative Cl2p → * resonance. The detailed chronology of the competing decay processes, leading to either the rearrangement product HCl + , or an ultrafast dissociation leading to Cl + , has been investigated. The observed Auger-Doppler shift has been analyzed for various orientations of the electron and fragment ion.
Laser Chemistry, 1995
Systematic behavior of decay rates of resonances above dissociation threshold is investigated by using the theory of resonance scattering. The condition for the Rice-Ramsperger-Kassel-Marcus (RRKM) rate formula to be valid is clarified by analyzing the random model of unimolecular dissociation. The decay rate averaged over many resonances agrees with the RRKM rate when the mean spacing and the mean width of the resonance states coincide with each other. On the other hand, auto- and mutual-correlation functions of the non-stationary wave functions indicate a rather paradoxical and intriguing phenomenon: In the RRKM regime, insufficient time is left for intramolecular vibrational energy redistribution (IVR) before dissociation.