Angular distribution and intensity in molecular photoelectron spectroscopy I. General theory for diatomic molecules

Buckingham, A. D.; Orr, Brian J.; Sichel, J. M.

doi:10.1016/b978-044482596-4/50033-6

Cited by 9 publications

(12 citation statements)

References 21 publications

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“…In a simple orbital-ionization model, the rotational branch structure of the photoelectron spectrum can be predicted from the angular-momentum characteristics of the electron hole generated in the molecule upon ionization. 31,32 The removal of an electron from the fully occupied 1π g HOMO of HCCCCH, which Ref. [34] for the analogous situation encountered in the PFI-ZEKE photoelectron spectrum of CO 2 .…”

Section: Resultsmentioning

confidence: 97%

Spin–orbit interaction and Renner–Teller effect in HCCCCH⁺studied by high-resolution photoelectron spectroscopy

Jacovella

Merkt

2017

Phys. Chem. Chem. Phys.

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The photoelectron spectra of the XΠ ← X Σ photoionizing transition of diacetylene (HCCCCH) and d2-diacetylene (DCCCCD) have been recorded at high resolution using the technique of pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy. The partially resolved rotational structure of the origin band of the spectra of HCCCCH and DCCCCD has enabled the determination of the adiabatic ionization energies of HCCCCH [E = 82072.2(5) cm] and DCCCCD [E = 82090.0(10) cm] and of the spin-orbit coupling constant [A = -31.1(4) cm] of the ground vibronic state of HCCCCH, which is smaller than the value of -33.3 cm commonly used since the work of Callomon (J. H. Callomon, Can. J. Phys., 1956, 34, 1046). Several excited vibrational levels of HCCCCH and DCCCCD, including some affected by the Renner-Teller effect and Fermi interactions, have been observed and the fundamental wavenumber of the mode ν has been determined in both HCCCCH (200.0(10) cm) and DCCCCD (192.6(20) cm). Possible assignments for several of these levels are discussed and deficiencies in the current understanding of the energy-level structure of the radical cation of diacetylene are pointed at.

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Section: Resultsmentioning

confidence: 97%

Spin–orbit interaction and Renner–Teller effect in HCCCCH⁺studied by high-resolution photoelectron spectroscopy

Jacovella

Merkt

2017

Phys. Chem. Chem. Phys.

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“…The orbital out of which the electron is ejected has the character of an s orbital centered on H − . A single center expansion of this orbital around the geometric center of the molecule is expected not to converge fast with increasing value of the orbital angular-momentum quantum number l and thus to give rise to large |∆N | values according to the propensity rule for photoionization ∆N ≤ |l| (14) obtained using the orbital-ionisation approximation [32,33]. The rotational progressions observed experimentally all obey the selection rule ∆N = even or odd for transitions to the X + 2 Σ + g or A + 2 Σ + u state, respectively, which is imposed by the conservation of nuclear-spin symmetry.…”

Section: Resultsmentioning

confidence: 99%

High-resolution photoelectron spectroscopy and calculations of the highest bound levels of ${{\rm{D}}}_{2}^{+}$ below the first dissociation threshold

Beyer¹,

Merkt²

2017

J. Phys. B: At. Mol. Opt. Phys.

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Pulsed-field ionization zero-kinetic-energy photoelectron spectra of D2 have been recorded from the intermediate H 1 Σ + g state to determine the positions of bound rovibronic levels of D + 2 located up to 1400 cm −1 below the D + + D(1s) dissociation threshold. The ion-pair character of the H intermediate state resulted in large changes ∆N = N + − N of the rotational quantum number upon photoionization, which enabled the observation of levels of D + 2 with rotational quantum number N + as high as 10. The experimental data cover a range of levels within which the usual hierarchy of timescales of the electronic, vibrational and rotational motions is inverted. The term values of these levels with respect to the X 1 Σ + g (v = 0, N = 0) rovibronic ground state of D2 and the energy intervals of the ionic states, measured with an accuracy of typically 0.11 cm −1 and 0.02 cm −1 , respectively, are compared with positions calculated ab-initio at various degrees of approximation, starting from the Born-Oppenheimer approximation and successively including adiabatic, nonadiabatic, relativistic and radiative corrections. The comparison shows that the accuracy of the photoelectron-spectroscopic measurement is sufficient to reveal the effects of the adiabatic, nonadiabatic, relativistic and radiative corrections on the absolute term values. Comparing our calculations, which rely on an approximate evaluation of the nonadiabatic corrections based on effective R-dependent reduced masses, with the theoretical results for N + ≤ 5 by Moss (J. Chem. Soc. Faraday Trans. 89, 3851 (1993)) and for N + ≤ 8 by Wolniewicz and Orlikowski (Mol. Phys. 74, 103 (1991)) enables the quantification of the errors introduced by our approximative treatment of the nonadiabatic corrections. Improved rotational term values of the H(v = 12) level were also derived.

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“…Until recently, no practical analog of the Cooper-Zare formula existed for photodetachment from MOs described by more than one value (97). Concepts similar to those that underlie the s&p partial-wave approach (Section 3) have led to an approximate formalism for photodetachment from mixed-character s-p states.…”

Section: Photodetachment From S-p Mixed-character Statesmentioning

confidence: 99%

Laboratory-Frame Photoelectron Angular Distributions in Anion Photodetachment: Insight into Electronic Structure and Intermolecular Interactions

Sanov

2014

Annu. Rev. Phys. Chem.

119

129

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This article provides an overview of some recent advances in the modeling of photoelectron angular distributions in negative-ion photodetachment. Building on the past developments in threshold photodetachment spectroscopy that first tackled the scaling of the partial cross sections with energy, depending on the angular momentum quantum number ℓ, it examines the corresponding formulation of the central potential model and extends it to the more general case of hybrid molecular orbitals. Several conceptual approaches to understanding photoelectron angular distributions are discussed. In one approach, the angular distributions are examined based on the contributions of the symmetry-allowed s and p partial waves of the photodetached electron. In another related approach, the parent molecular orbitals are described based on their dominant s and p characters, whereas the continuum electron is described in terms of interference of the corresponding Δℓ =±1 photodetachment channels.

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Angular distribution and intensity in molecular photoelectron spectroscopy I. General theory for diatomic molecules

Cited by 9 publications

References 21 publications

Spin–orbit interaction and Renner–Teller effect in HCCCCH⁺studied by high-resolution photoelectron spectroscopy

Spin–orbit interaction and Renner–Teller effect in HCCCCH⁺studied by high-resolution photoelectron spectroscopy

High-resolution photoelectron spectroscopy and calculations of the highest bound levels of ${{\rm{D}}}_{2}^{+}$ below the first dissociation threshold

Laboratory-Frame Photoelectron Angular Distributions in Anion Photodetachment: Insight into Electronic Structure and Intermolecular Interactions

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Angular distribution and intensity in molecular photoelectron spectroscopy I. General theory for diatomic molecules

Cited by 9 publications

References 21 publications

Spin–orbit interaction and Renner–Teller effect in HCCCCH+studied by high-resolution photoelectron spectroscopy

Spin–orbit interaction and Renner–Teller effect in HCCCCH+studied by high-resolution photoelectron spectroscopy

High-resolution photoelectron spectroscopy and calculations of the highest bound levels of ${{\rm{D}}}_{2}^{+}$ below the first dissociation threshold

Laboratory-Frame Photoelectron Angular Distributions in Anion Photodetachment: Insight into Electronic Structure and Intermolecular Interactions

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Spin–orbit interaction and Renner–Teller effect in HCCCCH⁺studied by high-resolution photoelectron spectroscopy

Spin–orbit interaction and Renner–Teller effect in HCCCCH⁺studied by high-resolution photoelectron spectroscopy