1887
banner image
No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
Rotationally resolved PFI-ZEKE photoelectron spectroscopic study of the low-lying electronic states of ArXe+
Rent:
Rent this article for
USD
10.1063/1.4747549
/content/aip/journal/jcp/137/9/10.1063/1.4747549
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/9/10.1063/1.4747549

Figures

Image of FIG. 1.
FIG. 1.

(a) Schematic molecular orbital diagram of ArXe arising from the 3p and 5p atomic valence orbitals of Ar and Xe, respectively. The electronic configurations and Hund's case (a) and (b) labels of the low-lying electronic states of ArXe+ one obtains by removing one electron from each of the molecular orbitals are indicated on the right-hand side. (b) Potential-energy functions of the six low-lying electronic states of ArXe+. The vertical line marks the equilibrium internuclear separation in the X 0+ neutral ground state. Adapted from Ref. 9.

Image of FIG. 2.
FIG. 2.

Generic patterns showing the rovibrational energy level structure of 2Σ+ states for (i) γ > 0, γ ≪ B; (ii) γ < 0, |γ| ≪ B; (iii) γ > 0, γ ≈ 2B; and (iv) γ < 0, |γ| ≈ 2B.

Image of FIG. 3.
FIG. 3.

Generic patterns showing the rovibrational energy level structure of 2Π states for (i) p > 0, pB; (ii) p < 0, |p| ≪ B; (iii) p > 0, p ≈ 2B; and (iv) p < 0; |p| ≈ 2B.

Image of FIG. 4.
FIG. 4.

REMPI spectrum of the D 0+ (v′ = 1) ← X 0+ (v = 0) transition of selected isotopomers of ArXe. The dashed vertical lines indicate the spectral positions used to selectively excite the J = 7, 10 and 13 levels of the D 0+ (v′ = 1) state of the 40Ar129Xe isotopomer. At these positions there is overlap with transitions of only one isotopomer.

Image of FIG. 5.
FIG. 5.

REMPI spectrum of the C 1 (v′ = 5) ← X 0+ (v = 0) transition of selected isotopomers of ArXe. The dashed vertical lines indicate the spectral positions used to selectively excite the J = 9, 10, 11 and 12 e-symmetry levels of the C 1 (v′ = 5) state of the 40Ar132Xe isotopomer. At these positions there is overlap with transitions of only one isotopomer.

Image of FIG. 6.
FIG. 6.

Rotationally resolved PFI-ZEKE photoelectron spectra of the A1 3/2 (v + = 0, 1, 2) levels of 40Ar129Xe (panel (a), recorded via the D 0+ v′ = 1 intermediate state), and of the A1 3/2 (v + = 3) level of 40Ar131Xe (panel (b), recorded via the C 1 (v′ = 5) intermediate state). In each panel, the experimental spectra are shown as lower, inverted traces and the calculated spectra as upper traces. The dotted vertical lines indicate the positions of the rotational levels of ArXe+. The lines corresponding to the ΔJ = J +J = 0.5 transitions are marked with asterisks.

Image of FIG. 7.
FIG. 7.

Rotationally resolved PFI-ZEKE photoelectron spectra of the A2 1/2 state of 40Ar132Xe. (a) Rotational structures of the v + = 0, 1, and 5 vibrational levels recorded via the D 0+ (v′ = 1,J = 12 (+)) intermediate state. (b) PFI-ZEKE photoelectron spectra of the A2 1/2 (v + = 2, 6) vibrational levels recorded via the C 1 (v′ = 5, J′ = 12 (+)) intermediate state and of the A2 1/2 (v + = 8) level recorded via the C 1 (v′ = 5, J′ = 9 (−)) intermediate state. The experimental spectra are shown as lower, inverted traces and the spectra calculated on the basis of propensity rules are depicted as upper traces (see text for details). The asterisks mark rotational lines that correspond to the overlapping ΔJ = J +J = −0.5 and ΔJ = (J + + 1) − J = 0.5 transitions.

Image of FIG. 8.
FIG. 8.

(a) Rotationally resolved PFI-ZEKE photoelectron spectra of the v + = 5 vibrational level of the A2 1/2 state of 40Ar132Xe recorded via the D 0+ (v′ = 1, J′ = 12( + ) and 13(−)) intermediate states. (b) A schematic excitation scheme from the J = 12(+), 13(−) intermediate levels to the overlapping Ω-doubling components of the J +(e) and (J + + 1)( f ) levels. The left-hand side of panel (b) corresponds to the case characterized by p ≈ 0 for which each J + rotational level of the A2 1/2 state consists of two closely spaced levels of opposite parity. The right-hand side of panel (b) corresponds to the case p ≈ −2B for which the rotational levels of the A2 1/2 state consist of closely spaced levels of the same parity. It is only for this second case that the experimentally observed intensity alternation can be explained using the parity selection rule (Eq. (8)) in combination with a dominant l = 1 partial wave expected following photoionization from the 6sσ[A2 1/2] component of the D 0+ level. The bold and dotted arrows indicate intense and weak transitions observed experimentally (see panel a)), respectively. The transitions from the intermediate J = 12, 13 rotational levels to the J + = 11.5(e/ −), 12.5(f /−) final levels are marked by the dashed line in panel (a) and correspond to the transitions indicated by the ellipse in panel (b).

Image of FIG. 9.
FIG. 9.

Rotationally resolved PFI-ZEKE photoelectron spectra of the v + = 5 (a) and 6 (b) vibrational levels of the X 1/2 state of 40Ar129Xe recorded via the D 0+ (v′ = 1, J′ = 10, 12, 14, 16) intermediate states. The lines corresponding to the overlapping ΔJ = J +J = −0.5 (where J + = N + − 1/2) and ΔJ = J +J = 1.5 (where J + = (N + + 1) + 1/2) transitions are marked with asterisks. (c) Schematic rotational energy level diagram of the X 1/2 state of ArXe+.

Image of FIG. 10.
FIG. 10.

Rotationally resolved PFI-ZEKE photoelectron spectra of the v + = 0, 2, 8, and 14 vibrational levels of the X 1/2 state of 40Ar132Xe recorded via the C 1 (v′ = 5, J′ = 10, 12, 17) intermediate levels. In each panel, the experimental spectra are shown as lower, inverted traces and the calculated spectra as upper traces. The second, upper calculated spectra presented for v + = 14 correspond to the second possible rotational assignment discussed in the text. The lines corresponding to the overlapping ΔJ = J +J = 0.5 (with J + = N + − 1/2) and ΔJ = J +J = 2.5 (with J + = (N + + 1) + 1/2) transitions are marked with an asterisk below the spectra (the cross marks the same transitions for the second possible assignment).

Tables

Generic image for table
Table I.

Expected ionization channels in the single-photon threshold ionization from the C and D states of ArXe as estimated from the photoionization and PFI-ZEKE photoelectron spectra reported in Ref. 9.

Generic image for table
Table II.

Vibronic term values and rotational constants of the A1 3/2 state of 40Ar129Xe+, 40Ar131Xe+, and 40Ar132Xe+ determined from the rotational analysis in Hund's coupling case (a).

Generic image for table
Table III.

Vibronic term values and rotational constants of the A2 1/2 state of 40Ar129Xe+ and 40Ar132Xe+ determined from the rotational analysis in Hund's coupling case (a).

Generic image for table
Table IV.

Vibronic term values and rotational constants of the X 1/2 state of 40Ar129Xe+ and 40Ar132Xe+ determined from the rotational analysis in Hund's coupling case (b).

Generic image for table
Table V.

Adiabatic ionization energies E i, dissociation energies , vibrational and anharmonicity constants, equilibrium rotational constants , vibration-rotation coupling constant , and the equilibrium internuclear separation of the lowest three electronic states of ArXe+. All values are in cm−1, except the internuclear distance which is given in Å.

Loading

Article metrics loading...

/content/aip/journal/jcp/137/9/10.1063/1.4747549
2012-09-06
2014-04-17
Loading

Full text loading...

This is a required field
Please enter a valid email address
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Rotationally resolved PFI-ZEKE photoelectron spectroscopic study of the low-lying electronic states of ArXe+
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/9/10.1063/1.4747549
10.1063/1.4747549
SEARCH_EXPAND_ITEM