Observation of anisotropic interactions between metastable atoms and target molecules by two-dimensional collisional ionization electron spectroscopy

Kishimoto, Naoki; Ohno, Koichi

doi:10.1080/01442350601053393

Cited by 22 publications

(23 citation statements)

References 179 publications

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“…For example, photoionization cross‐sections in the sudden approximation may be determined when T describes the interaction between a radiation field and electrons 3. Penning ionization cross‐sections for collisions between excited He atoms and molecules involve the electron repulsion operator 29. Transition probabilities that pertain to electron‐two‐electron scattering experiments invoke probability amplitudes corresponding to Dyson orbitals 30,31.…”

Section: Electron Propagator Conceptsmentioning

confidence: 99%

Electron propagator theory: an approach to prediction and interpretation in quantum chemistry

Ortiz

2012

WIREs Comput Mol Sci

190

194

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Electron propagator theory provides a practical means of calculating electron binding energies, Dyson orbitals, and ground‐state properties from first principles. This approach to ab initio electronic structure theory also facilitates the interpretation of its quantitative predictions in terms of concepts that closely resemble those of one‐electron theories. An explanation of the physical meaning of the electron propagator's poles and residues is followed by a discussion of its couplings to more complicated propagators. These relationships are exploited in superoperator theory and lead to a compact form of the electron propagator that is derived by matrix partitioning. Expressions for reference‐state properties, relationships to the extended Koopmans's theorem technique for evaluating electron binding energies, and connections between Dyson orbitals and transition probabilities follow from this discussion. The inverse form of the Dyson equation for the electron propagator leads to a strategy for obtaining electron binding energies and Dyson orbitals that generalizes the Hartree–Fock equations through the introduction of the self‐energy operator. All relaxation and correlation effects reside in this operator, which has an energy‐dependent, nonlocal form that is systematically improvable. Perturbative arguments produce several, convenient (e.g. partial third order, outer valence Green's function, and second‐order, transition‐operator) approximations for the evaluation of valence ionization energies, electron affinities, and core ionization energies. Renormalized approaches based on Hartree–Fock or approximate Brueckner orbitals are employed when correlation effects become qualitatively important. Reference‐state total energies based on contour integrals in the complex plane and gradients of electron binding energies enable exploration of final‐state potential energy surfaces. © 2012 John Wiley & Sons, Ltd. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods

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Section: Electron Propagator Conceptsmentioning

confidence: 99%

Electron propagator theory: an approach to prediction and interpretation in quantum chemistry

Ortiz

2012

WIREs Comput Mol Sci

190

194

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“…In particular, stimulated by the 2D-PIES of He * (2 3 S)-N 2 , CO, and CH 3 CN systems, Ohno and coworkers performed reliable ab initio calculations for both anisotropic entrance and exit potentials as well as for ionization probabilities (Yamazaki et al, 2002). After that, a series of important papers were published by Ohno group on this direction (Yamazaki et al, 2002, 2005, 2007; Ohno, 2004; Khishimoto and Ohno, 2007).…”

Section: Introductionmentioning

confidence: 99%

“…The basic novelty consists on the following two main points: (i) The radial dependence of the real part of the potential [V t in the Equation (1)], both in the entrance and exit channels, is represented by an Improved Lennard Jones Potential model (ILJ) defined by few parameters related to basic physical properties of the interacting particles (Pirani et al, 2008). Its reliability, tested on high resolution scattering and spectroscopic experiments as well as by ab initio calculations, has been found to be comparable and even better with respect to that of multiparameter functions, widely used in the past, as the TT model (Falcinelli et al, 2017); (ii) The description of the anisotropy in both channels in terms of the same components related to the selective dependence of CT on the half-filled P orbital alignment within the intermediate collision complex; (iii) The internally consistent representation of both real V t and imaginary Γ parts of the optical potential [see Equation (1)] which, for the first time, has been considered not independent (as it has been done until now) but interdependent being related to the selectivity of CT. Other relevant works in the stereodynamical investigation of auto-ionization processes have been carried out by Ohno and coworkers on the He * -molecule systems where the He * is an isotropic reagent and the dependence on the features of the involved molecular orbitals has been characterized (Ohno, 2004; Yamazaki et al, 2005, 2007; Horio et al, 2006; Khishimoto and Ohno, 2007). Important contributions have been also provided by the Kasai group on the dependence of reactions on the orientation of symmetric top molecules investigated in detail considering Ar * as an isotropic collisional partner (Yamato et al, 2000; Brunetti et al, 2001; Ohoyama et al, 2001).…”

Section: Introductionmentioning

confidence: 99%

A New Insight on Stereo-Dynamics of Penning Ionization Reactions

et al. 2019

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Recent developments in the experimental study of Penning ionization reactions are presented here to cast light on basic aspects of the stereo-dynamics of the microscopic mechanisms involved. They concern the dependence of the reaction probability on the relative orientation of the atomic and molecular orbitals of reagents and products. The focus is on collisions between metastable Ne * ( 3 P 2, 0 ) atoms with other noble gas atoms or molecules, for which play a crucial role both the inner open-shell structure of Ne * and the HOMO orbitals of the partner. Their mutual orientation with respect to the intermolecular axis controls the characteristics of the intermolecular potential, which drives the collision dynamics and the reaction probability. The investigation of ionization processes of water, the prototype of hydrogenated molecules, suggested that the ground state of water ion is produced when Ne * approaches H 2 O perpendicularly to its plane. Conversely, collisions addressed toward the lone pair, aligned along the water C 2v symmetry axis, generates electronically excited water ions. However, obtained results refer to a statistical/random orientation of the open shell ionic core of Ne * . Recently, the attention focused on the ionization of Kr or Xe by Ne * , for which we have been able to characterize the dependence on the collision energy of the branching ratio between probabilities of spin orbit resolved elementary processes. The combined analysis of measured PIES spectra suggested the occurrence of contributions from four different reaction channels, assigned to two distinct spin-orbit states of the Ne * ( 3 P 2, 0 ) reagent and two different spin-orbit states of the ionic M + ( 2 P 3/2, 1/2 ) products (M = Kr, Xe). The obtained results emphasized the reactivity change of 3 P 0 atoms with respect to 3 P 2 , in producing ions in 2 P 3/2 and 2 P 1/2 sublevels, as a function of the collision energy. These findings have been assumed to arise from a critical balance of adiabatic and non-adiabatic effects that control formation and electronic rearrangement of the collision complex, respectively. From these results we are able to characterize for the first time, according to our knowledge, the state to state reaction probability for the ionization of Kr and Xe by Ne * in both 3 P 2 and 3 P 0 sublevels.

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“…In contrast to the extensive studies on the reaction dynamics for the electronically excited atoms, − the studies on the reaction dynamics for the electronically excited molecules have been extremely limited. The molecular–molecular reactions involving an electronically excited molecule are fundamental processes in the chemistry such as of the upper atmosphere, combustion, photonic synthesis, and so on .…”

Section: Introductionmentioning

confidence: 99%

Collision Energy Dependent Cross Section and Rotational Alignment of NO (A ²Σ⁺) in the Energy-Transfer Reaction of N₂ (A³Σ_u⁺) + NO (X ²Π) → N₂ (X ¹Σ_g⁺) + NO (A ²Σ⁺)

Ohoyama

2014

J. Phys. Chem. A

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We have studied the collision energy dependent cross section and alignment of NO (A (2)Σ(+)) rotation in the energy-transfer reaction of N2 (A (3)Σ(u)(+)) + NO (X (2)Π) → N2 (X (1)Σ(g)(+)) + NO (A (2)Σ(+)) at the collision energy (E) region of 0.03-0.2 eV. NO (A (2)Σ(+)) emission in two linear polarization directions in the collision frame (parallel (∥) and perpendicular (⊥) with respect to the relative velocity vector (vR)) has been measured as a function of collision energy. NO (A (2)Σ(+)) rotation (J-vector) turns out to be aligned perpendicular to vR. In addition, collision energy is found to enhance the degree of alignment of NO (A (2)Σ(+)) rotation. The collision energy dependent cross sections σ(∥,(⊥))(E) (excitation functions) show a rapid fall-off following an initial rise with a threshold less than 0.02 eV. The excitation function at the parallel alignment of NO (A (2)Σ(+)) rotation, σ(J∥v(R), (E), is slightly shifted to the low collision energy region as compared with σ(J ⊥ vR, E). We propose that the rapid fall-off feature in the excitation function is attributed to the multidimensional nonadiabatic transitions.

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Observation of anisotropic interactions between metastable atoms and target molecules by two-dimensional collisional ionization electron spectroscopy

Cited by 22 publications

References 179 publications

Electron propagator theory: an approach to prediction and interpretation in quantum chemistry

Electron propagator theory: an approach to prediction and interpretation in quantum chemistry

A New Insight on Stereo-Dynamics of Penning Ionization Reactions

Collision Energy Dependent Cross Section and Rotational Alignment of NO (A ²Σ⁺) in the Energy-Transfer Reaction of N₂ (A³Σ_u⁺) + NO (X ²Π) → N₂ (X ¹Σ_g⁺) + NO (A ²Σ⁺)

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Observation of anisotropic interactions between metastable atoms and target molecules by two-dimensional collisional ionization electron spectroscopy

Cited by 22 publications

References 179 publications

Electron propagator theory: an approach to prediction and interpretation in quantum chemistry

Electron propagator theory: an approach to prediction and interpretation in quantum chemistry

A New Insight on Stereo-Dynamics of Penning Ionization Reactions

Collision Energy Dependent Cross Section and Rotational Alignment of NO (A 2Σ+) in the Energy-Transfer Reaction of N2 (A3Σu+) + NO (X 2Π) → N2 (X 1Σg+) + NO (A 2Σ+)

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Collision Energy Dependent Cross Section and Rotational Alignment of NO (A ²Σ⁺) in the Energy-Transfer Reaction of N₂ (A³Σ_u⁺) + NO (X ²Π) → N₂ (X ¹Σ_g⁺) + NO (A ²Σ⁺)