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Photoelectron spectroscopic study of the E ⊗ e Jahn-Teller effect in the presence of a tunable spin-orbit interaction. III. Two-state excitonic model accounting for observed trends in the ground state of and
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10.1063/1.4745002
/content/aip/journal/jcp/137/8/10.1063/1.4745002
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/8/10.1063/1.4745002

Figures

Image of FIG. 1.
FIG. 1.

Photoelectron spectra of the , , and transitions of , , , and CH3I (top to bottom panels) recorded by Karlsson and co-workers.7 Adapted from Ref. 7.

Image of FIG. 2.
FIG. 2.

High-resolution PFI-ZEKE photoelectron spectrum of the transition of in the region of the vibronic ground state of (top panel), and the corresponding calculation shown as stick spectrum (bottom panel) and after convolution with a Gaussian line profile with a FWHM of 0.8 cm−1 representing the instrumental linewidth (middle panel). The experimental spectrum has not been corrected for the field-induced shift (≈−0.84 cm−1) of the ionization energies. The assignment bars label the most intense ΔN = 0 transitions of the dominant (ΔK = K +K = +1) and the minor (ΔK = K +K = −2) contributions to the vibronic wavefunction induced by the Jahn-Teller effect.

Image of FIG. 3.
FIG. 3.

Schematic diagram of the two-state excitonic model, where either methane (left-hand side) or the halogen atom (right-hand side) is ionized and becomes the electron donor. The gray horizontal lines mark the eigenvalues of the excitonic coupling matrix H exc obtained using Eq. (6) which correspond to the lowest and a higher lying 2E electronic state in the methyl-halide cation. The ionization energies E I are indicated by vertical arrows.

Image of FIG. 4.
FIG. 4.

Energy differences between calculated and experimental ionization energies of the methyl-halide cations as a function of the interaction potential V exc. The ΔE I of the lower (E I) and upper 2E electronic states are decreasing and increasing in energy for an increasing interaction potential V exc, respectively. The states from to are shown as black to gray lines of decreasing blackness, and is shown as dotted line because of the large uncertainty in the experimental determination of this ionization energy. The dashed vertical line (V exc = 17 500 cm−1) marks the strength of the interaction potential where ΔE I and are minimized.

Image of FIG. 5.
FIG. 5.

Schematic energy diagram presenting the ionization energies E I of methane and the halogen atoms (black vertical arrows), which are coupled by the excitonic matrix H exc (Eq. (6)) by an interaction potential V exc = 17 500 cm−1. The resulting eigenvalues, which represent the lowest and a higher lying 2E state in the methyl-halide cations, are marked by gray horizontal lines, and the corresponding experimental ionization energies66 are marked by black horizontal lines. The energy of the upper 2E electronic state of derived from photoelectron spectra7,66 is marked by a dotted line, because there is a large experimental uncertainty to its energy, see text for details.

Image of FIG. 6.
FIG. 6.

Schematic energy diagram presenting the ionization energies E I of methane and of atomic oxygen and sulphur (black vertical arrows), which are coupled in the excitonic matrix H exc (Eq. (6)) by an interaction potential V exc = 17 500 cm−1. The resulting eigenvalues are marked by gray horizontal lines, and the corresponding experimental ionization energies67,68 are marked by black horizontal lines.

Image of FIG. 7.
FIG. 7.

Schematic energy diagram presenting the electron affinities EA of methane62 and of atomic oxygen and sulphur69 (black vertical arrows), which are coupled in the excitonic matrix (Eq. (10)) by an interaction potential V exc = 17 500 cm−1. The resulting eigenvalues are marked by gray horizontal lines, and the corresponding experimental electron affinities63,64 are marked by black horizontal lines.

Tables

Generic image for table
Table I.

Allowed rovibronic transitions in a photoionizing transition in the molecular symmetry group . The selection rules are the same for even-ℓ and odd-ℓ photoelectron partial waves.

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Table II.

Spin-orbit coupling in the 2E ground state of and .

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Table III.

Main Jahn-Teller coupling parameters in the 2E ground state of and .

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Table IV.

Harmonic wave numbers (in cm−1) of the six vibrational modes of , , and in C3v symmetry.

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Table V.

Atomic ionization energies55–57 (in cm−1), determined as the center-of-gravity energies of the neutral and ionic states, and vertical ionization energy of methane58,59 (in cm−1).

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Table VI.

Ionization energies and ( and ) to the lowest and a higher lying electronic state of (CH3Y+), determined from photoelectron spectroscopic studies (“Experiment”) and with the exciton-type model of Eq. (6) using an interaction potential V exc = 17 500 cm−1 (“Model”). In the last two columns, the differences between the calculated and experimentally determined ionization energies (ΔE I and ) are presented.

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Table VII.

Values of a X(Y), , and , determined with V exc = 17 500 cm−1, and the comparison to ζe of the 2E ground states of and .

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Table VIII.

Electron affinities for the chalcogen atoms,69 methane,62 ,63 and CH3S (Ref. 64) (in cm−1).

Generic image for table
Table IX.

Values of EA, , , and , determined with V exc = 17 500 cm−1, and the comparison to ζe of the 2E ground state of .

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/content/aip/journal/jcp/137/8/10.1063/1.4745002
2012-08-29
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Photoelectron spectroscopic study of the E ⊗ e Jahn-Teller effect in the presence of a tunable spin-orbit interaction. III. Two-state excitonic model accounting for observed trends in the X̃2E ground state of CH 3X+(X=F, Cl , Br ,I) and CH 3Y(Y=O,S)
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/8/10.1063/1.4745002
10.1063/1.4745002
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