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Two-dimensional resonance enhanced multiphoton ionization of HCl: State interactions and photorupture channels via low-energy triplet Rydberg states
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10.1063/1.3180824
/content/aip/journal/jcp/131/4/10.1063/1.3180824
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/4/10.1063/1.3180824

Figures

Image of FIG. 1.
FIG. 1.

Ionization mechanisms. Schematics (a) and (b) showing possible ionization channels following excitations and/or state transfer (1) to a diabatic Rydberg state [channels (i), (ii), and (ix)], (2) to a hypothetical diabatic ion-pair state [channels (iii)–(vii)], and (3) to neutral fragments via predissociation of a gateway Rydberg state (viii). The arrows represent excitations relevant to REMPI. Fragments and excited state species are indicated. The ions formed are highlighted with circles. The total number of photons is indicated.

Image of FIG. 2.
FIG. 2.

(a) 1D REMPI spectra for , , , , and derived from HCl with isotope ratios in natural abundance for the two-photon excitation region of . Assignments for the , (0,0), line and , (8,0), line transitions are shown. (b) 2D REMPI contour (below) for chlorine-containing ions and 1D REMPI spectra (above) for , , , and derived from HCl with isotope ratios in natural abundance for the two-photon excitation region of . Assignments for the , (0,0), line transitions are shown. -numbers are indicated in the figures.

Image of FIG. 3.
FIG. 3.

(a) 1D REMPI spectra for , , , , and derived from HCl with isotope ratios in natural abundance for the two-photon excitation region of . Assignments for the , (0,0), line and , (9,0), line and (0,0), line transitions are shown. (b) 1D REMPI spectra for and for the region of . Assignments for the , (0,0), line and the , (0,0), , line transitions are shown. -numbers are indicated in the figures.

Image of FIG. 4.
FIG. 4.

Relative (normalized) ion signal intensities, (a) for , (0,0), derived from the following: (i) rotational lines (white columns), (ii) lines (black columns), and (iii) simulations of the data for the lines, marked as “calc.” (gray columns; see text). (b) and for , (8,0), derived from lines. Ratios for could not be derived because of rotational line overlapping. (c) for , (0,0), derived from the following: (i) lines (white columns), (ii) lines (black columns), and (iii) simulations of the data for the lines, marked as calc. (gray columns; see text). (d) for , (0,0), derived from the following: (i) lines (white columns), (ii) simulations of the data for the lines, marked as calc. (gray columns; see text). (e) and for , (9,0), derived from lines.

Image of FIG. 5.
FIG. 5.

Schematic energy levels marked with parities (±) and relevant quantum numbers and selected two-photon transitions for the and electronic transitions and the and rotational transitions. Selection rules relevant to two-photon transitions and state interactions are indicated at the bottom right corner of the figure. According to the selection rules, only the state component of the state is accessed by the and rotational transitions whereas the state components of the excited states are accessed by the , , and transitions. Based on the selection rules for state interactions, only crossing between states components can occur.

Tables

Generic image for table
Table I.

Rotational lines of relevant transitions derived by Green et al. (Ref. 9) (marked “others”) and us (“ours”) . The accuracy of “our” values is about .

Generic image for table
Table II.

relevant to near-resonance interactions for , , , , and , .

Generic image for table
Table III.

Parameter values in the least square fit model for ion intensity ratios as a function of ; see Eq. (7), related equations, and discussion Sec. III B.

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/content/aip/journal/jcp/131/4/10.1063/1.3180824
2009-07-29
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Two-dimensional (2+n) resonance enhanced multiphoton ionization of HCl: State interactions and photorupture channels via low-energy triplet Rydberg states
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/4/10.1063/1.3180824
10.1063/1.3180824
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