Vibrational branching ratios in photoionization of CO and N2

Rathbone, G. J.; Rao, R. Shyama Prasad; Poliakoff, E. D.; Wang, Kwanghsi; McKoy, Vincent

doi:10.1063/1.1631818

Cited by 7 publications

(11 citation statements)

References 29 publications

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“…At higher energies the RCHF approximation has also been used (CO 43,44,50,52,54,67,[115][116][117][118][119][120] , N 2 3 ). This is in contrast with the frozen core Hartree Fock (FCHF) approximation, which has widely been used in most earlier and some recent works (CO 42,48,58,74,75,106,121 , N 2 22,27,32,58,74,75,106 ).…”

Section: Theoretical Methods Within the Fixed-nuclei Approximationmentioning

confidence: 90%

“…Only a few methods described in the previous section have been used to study vibrationally resolved photoionization of CO 13,43,50,52,54,55,58,[65][66][67][68]78 and N 2 13,30,35,58,60,61,63,64,69-71,78 , and almost none in the region of high photon energies 78 . The reason is that one has to evaluate electronic continuum wave functions and potential energy curves in a dense grid of internuclear distances, which makes most methods prohibitively expensive.…”

Section: Dft-like Methods That Account For Molecular Vibrationmentioning

confidence: 99%

“…However, most of these studies have focused on the valence low-energy region and on the effect of shape resonances in vibrational branching ratios. Only a few of these studies have been performed in the high energy region 58,74,75 . More recent theoretical investigations have addressed the features appearing in the photoelectron spectra at high energy, mostly in core photoionization.…”

Section: Introductionmentioning

confidence: 99%

“…In particular, a wealth of experimental and theoretical data has been published for total cross sections corresponding to core as well as valence-shell photoionization of the prototype N 2 1-35 and CO 1,2,5,6,12,13,34,[36][37][38][39][40][41][42][43][44][45][46][47][48][49] molecules, from the ionization threshold up to a few tens of eV above it. More recently, the advent of high-brilliance 3rd-generation synchrotron radiation sources in combination with high energy-resolution detection techniques has opened the way for the determination of vibrationally resolved photoionization spectra of these molecules, both at low and high photon energies 30,35,38,39,[50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] . These experimental achievements have fostered the development of new theoretical methods that, in addition to accounting for electronic degrees of freedom, are also able to describe the molecule's vibrations 13,30,35,…”

Section: Introductionmentioning

confidence: 99%

“…More recently, the advent of high-brilliance 3rd-generation synchrotron radiation sources in combination with high energy-resolution detection techniques has opened the way for the determination of vibrationally resolved photoionization spectra of these molecules, both at low and high photon energies 30,35,38,39,[50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] . These experimental achievements have fostered the development of new theoretical methods that, in addition to accounting for electronic degrees of freedom, are also able to describe the molecule's vibrations 13,30,35,43,50,52,54,55,58,60,61,[63][64][65][66][67][68][69][70][71] .…”

Section: Introductionmentioning

confidence: 99%

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Vibrational branching ratios in the photoelectron spectra of N2 and CO: interference and diffraction effects

Plésiat

Decleva

Martín

2012

Phys. Chem. Chem. Phys.

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Esta es la versión de autor del artículo publicado en: This is an author produced version of a paper published in: We present a detailed account of existing theoretical methods specially designed to provide vibrationally resolved photoionization cross sections of simple molecules within the Born-Oppenheimer approximation, with emphasis on newly developed methods based on density functional theory. The performance of these methods is shown for the case of N 2 and CO photoionization. Particular attention is paid to the region of high photon energies, where the electron wavelength is comparable to the bond length and, therefore, two-center interferences and diffraction are expected to occur. As shown in a recent work [Canton et al., Proc. Natl. Acad. Sci., 2011, 108, 73027306], the main experimental difficulty, which is to extract the relatively small diffraction features from the rapidly decreasing cross section, can be easily overcome by determining ratios of vibrationally resolved photoelectron spectra and existing theoretical calculations. From these ratios, one can thus get direct information about the molecular geometry. In this work, results obtained in a wide range of photon energies and for many different molecular orbitals of N 2 and CO are discussed and compared with the available experimental measurements. From this comparison, limitations and further possible improvements of the existing theoretical methods are discussed. The new results presented in the manuscript confirm that the conclusions reported in the above reference are of general validity.

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