Theoretical spectroscopy of acetylene dication and its deuterated species

Palaudoux, J.; Jutier, Laurent; Hochlaf, M.

doi:10.1063/1.3431625

Cited by 5 publications

(5 citation statements)

References 36 publications

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“…kT , where m i and g are the reduced mass and degeneracy of the stretch and trans-bending motion are taken as 7 amu and 2.592 amu from spectroscopic data. 16 For simplicity, we assume all recoil energy of 0.012 eV is pumped into the transbending degrees of freedom (DOF), which will overestimate the likelihood of transbending. The rest of the kinetic energy E KER − E KER,CC is equally distributed among the five DOFs.…”

Section: Supplementarymentioning

confidence: 99%

“…The reason for this disparity is an apparent contradiction between theory and experiment, prompting numerous studies. 5,[12][13][14][15][16][17][18] Arguments on both sides can be summed up as follows. Experimental synchrotron data concludes that isomerization occurs on the low lying dicationic states 1 Σ g and 1 Δ g with vacancies 1πu -2 , while deprotonation and symmetric breakup occur on the higher lying 1 Π u states with 1πu -1 3σg -1 character.…”

Section: Introductionmentioning

confidence: 99%

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Ultrafast isomerization in acetylene dication after carbon K-shell ionization

Inhester

Liekhus-Schmaltz

et al. 2017

Nat Commun

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Ultrafast proton migration and isomerization are key processes for acetylene and its ions. However, the mechanism for ultrafast isomerization of acetylene [HCCH]2+ to vinylidene [H2CC]2+ dication remains nebulous. Theoretical studies show a large potential barrier ( > 2 eV) for isomerization on low-lying dicationic states, implying picosecond or longer isomerization timescales. However, a recent experiment at a femtosecond X-ray free-electron laser suggests sub-100 fs isomerization. Here we address this contradiction with a complete theoretical study of the dynamics of acetylene dication produced by Auger decay after X-ray photoionization of the carbon atom K shell. We find no sub-100 fs isomerization, while reproducing the salient features of the time-resolved Coulomb imaging experiment. This work resolves the seeming contradiction between experiment and theory and also calls for careful interpretation of structural information from the widely applied Coulomb momentum imaging method.

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Section: Supplementarymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ultrafast isomerization in acetylene dication after carbon K-shell ionization

Inhester

Liekhus-Schmaltz

et al. 2017

Nat Commun

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“…6, seem to have potential wells that may support a number of long-lived vibrational levels. Third, both Palaudoux and Furuhashi [15,55] have reported vibrational levels in similar dication states of acetylene, though the potential wells in the acetylene dication are about 1 eV deeper than in the ethylene dication.…”

Section: Summary: Ethylene Photo Double Ionizationmentioning

confidence: 99%

Photo-double-ionization of ethylene and acetylene near threshold

Gaire¹,

Lee²,

Haxton³

et al. 2014

Phys. Rev. A

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We present kinematically complete measurements of the photo double ionization of ethylene (double CC bond) and acetylene (triple CC bond) hydrocarbons just above the double ionization threshold. We discuss the results in terms of the coincident kinetic energy of the photo electrons and the nuclear kinetic energy release of the recoiling ions. We have incorporated quantum chemistry calculations to interpret which of the electronic states of the dication have been populated and trace the various subsequent fragmentation channels. We suggest pathways that involve the electronic ground and excited states of the precursor ethylene dication and explore the strong influence of the conical intersections between the different electronic states. The nondissociative ionization yield is small in ethylene and high in acetylene when compared with the dissociative ionization channels.The reason for such a striking difference is explained in part on the basis of a propensity rule which influences the population of states in the photo double ionization of a centrosymmetric closed shell molecule by favoring singlet ungerade and triplet gerade final states. This propensity rule and the calculated potential energy surfaces clarify a picture of the dynamics leading to the observed dication dissociation products.

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“…49,50 Recent developments dealing with the treatment of nuclear motions of tetratomic molecules using variational approaches and in full dimensionality (including Renner-Teller and spin orbit couplings) should allow to overcome such difficulties. [51][52][53][54] They could give an accurate prediction for the OMgOO + (X 2 P) spin-rovibronic spectrum. 44…”

Section: Pccp Papermentioning

confidence: 98%

Generation of full dimensional potential energy surfaces for atmospherically important charge transfer tetratomic complexes: the case of the OMgOO+ radical cation

Yazidi¹,

Hochlaf²

2013

Phys. Chem. Chem. Phys.

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The weakly bound charge transfer OMgOO(+)((2)Π) ion is a quasi-linear-bent Renner-Teller system with a non-zero spin-orbit contribution. The six-dimensional potential energy surfaces (6D-PESs) for the two Renner-Teller components have been generated in internal coordinates. After benchmarking calculations, we show that the newly implemented explicitly correlated coupled cluster approach (RCCSD(T)-F12) in connection with the cc-pVTZ-F12 basis set provides an accurate description of the full 6D-PESs of this molecular system. Both components are bent with low barriers to linearity along the in-plane angles. The potentials are also very flat along the out-of-plane torsional mode. Hence, this confers a pronounced quasi linear character to OMgOO(+). Moreover, the parts of the potentials relative to the middle bond are shallow and strongly coupled to the bending motions. The parts of the PESs corresponding to the OO and MgO external diatom stretch coordinates differ strongly from those relative to the four other internal coordinates. Special care was taken to correctly account for such behaviors during the generation of the grid and fitting procedures. The present theoretical methodology can be used for mapping the 6D-PESs of other atmospherically important charge transfer complexes presenting similar features such as ONNO(+), O4(+), OOCO(+) or M-CO2(+) (where M is an alkali, magnesium or aluminum metal).

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Theoretical spectroscopy of acetylene dication and its deuterated species

Cited by 5 publications

References 36 publications

Ultrafast isomerization in acetylene dication after carbon K-shell ionization

Ultrafast isomerization in acetylene dication after carbon K-shell ionization

Photo-double-ionization of ethylene and acetylene near threshold

Generation of full dimensional potential energy surfaces for atmospherically important charge transfer tetratomic complexes: the case of the OMgOO+ radical cation

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