<i>Ab initio</i>analysis of autoionization of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">H</mml:mi></mml:mrow><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>molecules using multichannel quantum-defect theory and new quantum-defect surfaces

Mistrik, I.; Reichle, R.; Müller, Ulrich; Helm, H.; Jungen, Martin; Stephens, J. A.

doi:10.1103/physreva.61.033410

Cited by 45 publications

(94 citation statements)

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“…This work was soon followed by the computations of Nager & Jungen [8], who used their frozen-core Rydberg ab initio method to predict numerous Rydberg states over a wide range of geometries. More recent potential surfaces of H 3 Rydberg states have been published in Mistrík et al [6] and Galster et al [19]. Among these, the highly correlated electronic wave functions and energies [6] obtained with the multi-reference code of Fink & Staemmler [20] based on the coupled electronpair approximation (CEPA) probably remain the most accurate values available today, and we shall use them below in an attempt to reevaluate the JT parameters of the npe , n = 3−5 Rydberg states.…”

Section: Theoretical Considerationsmentioning

confidence: 99%

“…The ab initio work on excited states of H 3 and H + 3 has been reported alternatively in terms of Dykstra coordinates [6,8,21], hyperspherical coordinates [19] or mass-scaled Jacobi coordinates [22]. In all these papers, the relationships between coordinates employed and the straightforward bond-length coordinates R 1 , R 2 , R 3 have been spelled out in detail.…”

Section: (A) Bond Lengths Versus Symmetry-adapted Coordinatesmentioning

confidence: 99%

“…We have used the ab initio 3pe surfaces from Mistrík et al [6] and Galster et al [19] in order to reexamine the JT parameters relevant for the npe Rydberg channel. This task has been performed previously by Staib & Domcke [7] on the basis of the theoretical surfaces from Nager & Jungen [8], and more recently by Mistrík et al [6] based on the new potential surfaces computed there.…”

Section: (C) Analysis Of N = 3 Ab Initio Potential Surfacesmentioning

confidence: 99%

“…We also attempt to redetermine the linear and quadratic JT splitting constants on the basis of the most sophisticated ab initio H 3 3pe potential surfaces existing to date. Although King & Morokuma [18] extracted a quadratic JT constant from their ab initio surface, to date, no quadratic constant for the later ab initio surfaces [6,8,19] has been reported; similarly, no quadratic constant has been extracted from the spectroscopic data of Herzberg et al [11,12]. While we focus in this work on the 3pe state of H 3 , we also consider the n = 4 and n = 5 members of the npe Rydberg series, for which ab initio potential energy surfaces also exist [6]; consideration of these surfaces provides information on the energy dependences of the quantum defect parameters.…”

Section: Introductionmentioning

confidence: 99%

“…The theory presented in Kokoouline et al [1] and dos Santos et al [2] is based on ab initio computations of bound n = 4 Rydberg states of H 3 by Mistrík et al [6], from which the static linear JT splitting was extracted, using a procedure initiated by Staib & Domcke [7] (who based their work on earlier ab initio computations of Nager & Jungen [8] for n = 3). This information then subsequently served to compute the dynamical electron capture process by the positive ion, followed by neutral molecular dissociation [2].…”

Section: Introductionmentioning

confidence: 99%

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The Jahn–Teller effect in the 3 pe ′ Rydberg state of H ₃ : review of experimental and ab initio determinations

Jungen

Pratt

2012

Phil. Trans. R. Soc. A.

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The dissociative recombination (DR) of H + 3 ions with electrons, producing neutral atomic and molecular fragments, is driven primarily by the vibronic Jahn-Teller (JT) interaction between the electronic components of the pe e − -H + 3 collision (Rydberg) channel. The JT parameters characterizing this interaction are therefore of great interest as they are required for the theoretical predictions of the DR cross section. In this contribution, we review various determinations of these quantities that have been made previously, based both on spectroscopic studies of 3pe Rydberg-excited H 3 states, and on the analysis of the corresponding ab initio H 3 Rydberg potential surfaces near the conical intersection (D 3h symmetry) for n = 3 − 5. The highly correlated theoretical 3pe potential surfaces of Mistrík et al. are used for a new determination of both the linear and quadratic JT terms.

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Section: Theoretical Considerationsmentioning

confidence: 99%

Section: (A) Bond Lengths Versus Symmetry-adapted Coordinatesmentioning

confidence: 99%

Section: (C) Analysis Of N = 3 Ab Initio Potential Surfacesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Jahn–Teller effect in the 3 pe ′ Rydberg state of H ₃ : review of experimental and ab initio determinations

Jungen

Pratt

2012

Phil. Trans. R. Soc. A.

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Potential Energy Surfaces for the Na(3p)N2, Na(3p)HCN and Na(3p)C2H2 Complexes:Ab Initio Calculations and Model Considerations

Jungen

2001

HCA

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Dedicated to Prof. Edgar Heilbronner on the occasion of his 80th birthday Motto: Hier kocht der Chef, kommen Sie dennoch! Highly correlated ab initio calculations for the potential-energy surfaces of the systems NaÀN 2 , NaÀHCN, and NaÀC 2 H 2 have been performed, where the Na atom is in the 3s ground state or in the 3p excited state, and the molecules are kept fixed in their equilibrium configurations. The purpose of these calculations was to enable computer simulation of optical-scattering experiments. In this paper, model considerations are presented that allow easy qualitative understanding of the shapes of the calculated surfaces.Introduction. ± Modern quantum chemistry is a field of both physics and chemistry. No need to discuss its chemical merits in this journal. But surprisingly often also for the interpretation of physical experiments on systems more complex than an atom and less complex than a crystal, quantum chemistry can also make significant contributions. Various kinds of results based on precise numerical calculation of molecular wave functions are required. A few recent examples from my own work, where transition probabilities [1], quantum-defect surfaces [2], or spectroscopic assignments [3] were needed, may illustrate the situation. However, with increasing precision of quantumchemical results their transparency is lost, and while the results must be accepted, physical understanding can often not account for every numerical detail. The present study was carried out to support the interpretation of optical-collision experiments with molecules [4], providing high-precision interaction potentials for intermolecular forces in electronically excited states, and a physical interpretation of the results is attempted.One great advantage of quantum chemistry is the use of atomic units (a.u.) throughout, quantities are given in a.u. Conversion factors: length: 1 a o 5.29181 0 À11 m; energies: 1 a.u. 4.3598´10 À18 J; dipole moments: 1 a.u. 8.4783´10 À30 Cm; quadrupole moments: 1 a.u. 4.4865´10 À40 Cm 2 .

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High‐resolution Valence‐shell Photoionization

Pratt

2011

Handbook of High‐resolution Spectroscopy

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This article presents a brief review of high‐resolution, valence‐shell photoionization studies of diatomic and small polyatomic molecules. Both single‐photon ionization of ground‐state molecules and multiphoton/multistep ionization of excited‐state molecules are discussed, and the complementary nature of the two approaches is emphasized. Although direct photoionization processes are discussed, the principal focus of the article is on resonance phenomena such as autoionization and predissociation, with a particular emphasis on the former. The various forms of autoionization are illustrated by using examples from recent work on H 2 , H 3 , N 2 , NO, CO 2 , and other molecules.

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Ab initioanalysis of autoionization ofH3molecules using multichannel quantum-defect theory and new quantum-defect surfaces

Cited by 45 publications

References 51 publications

The Jahn–Teller effect in the 3 pe ′ Rydberg state of H ₃ : review of experimental and ab initio determinations

The Jahn–Teller effect in the 3 pe ′ Rydberg state of H ₃ : review of experimental and ab initio determinations

Potential Energy Surfaces for the Na(3p)N2, Na(3p)HCN and Na(3p)C2H2 Complexes:Ab Initio Calculations and Model Considerations

High‐resolution Valence‐shell Photoionization

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Ab initioanalysis of autoionization ofH3molecules using multichannel quantum-defect theory and new quantum-defect surfaces

Cited by 45 publications

References 51 publications

The Jahn–Teller effect in the 3 pe ′ Rydberg state of H 3 : review of experimental and ab initio determinations

The Jahn–Teller effect in the 3 pe ′ Rydberg state of H 3 : review of experimental and ab initio determinations

Potential Energy Surfaces for the Na(3p)N2, Na(3p)HCN and Na(3p)C2H2 Complexes:Ab Initio Calculations and Model Considerations

High‐resolution Valence‐shell Photoionization

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The Jahn–Teller effect in the 3 pe ′ Rydberg state of H ₃ : review of experimental and ab initio determinations

The Jahn–Teller effect in the 3 pe ′ Rydberg state of H ₃ : review of experimental and ab initio determinations