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Photofragmentations, state interactions, and energetics of Rydberg and ion-pair states: Resonance enhanced multiphoton ionization via E and V (B) states of HCl and HBr
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10.1063/1.4776260
/content/aip/journal/jcp/138/4/10.1063/1.4776260
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/4/10.1063/1.4776260

Figures

Image of FIG. 1.
FIG. 1.

(a) and (b) HCl: 1D REMPI spectra for H+, 35Cl+, H35Cl+ and J′ assignments for rotational peaks corresponding to two-photon resonance excitations to the E 1Σ+(v′ = 0, 1), V 1Σ+(v′ = 10, 11, 14, 15) and g 3Σ(v′ = 1) states for the excitation regions 83 200–84 250 cm−1 (a) and 85 600–86 440 cm−1 (b). (c) HBr: 1D REMPI spectra for H+, 79Br+, H79Br+ and J′ assignments for rotational peaks corresponding to two-photon resonance excitations to the E 1Σ+(v′ = 0), V 1Σ+(v′ = m + 4, m + 5) and i 3Δ3(v′ = 0) states for the excitation region 77 520–78 450 cm−1.

Image of FIG. 2.
FIG. 2.

HCl: Rotational energy levels, derived from the observed REMPI rotational peaks for the E 1Σ+(v′ = 1) and V 1Σ+(v′ = 14, 15) states. Level-to-level off-resonance interactions between the V(v′) ion-pair states and the E(v′) Rydberg states are indicated by broken lines. Strength and alterations in state mixings are indicated, roughly, by varying thickness of broken lines.

Image of FIG. 3.
FIG. 3.

(a) and (b) H35Cl: Spacings between rotational levels (ΔE J ′,J′−1) as a function of J′ for V 1Σ+(v′ = 15) ((a), top), E 1Σ+(v′ = 1) ((a), middle), V 1Σ+(v′ = 14) ((a), bottom), V 1Σ+(v′ = 11) ((b), top), E 1Σ+(v′ = 0) ((b), middle) and V 1Σ+(v′ = 10) ((b), bottom). (c) H79Br: Spacings between rotational levels (ΔE J ′,J′−1) as a function of J′ for V 1Σ+(v′ = m + 5) ((c), top), E 1Σ+(v′ = 0) ((c), middle) and V 1Σ+(v′ = m + 4) ((c), bottom). Open circles are derived from observed Q lines (this work and Refs. 2 and 5 , and 8 ). Filled circles are derived from deperturbation calculations (see text).

Image of FIG. 4.
FIG. 4.

(a) and (b) H35Cl: Relative ion signal intensities, I(35Cl+)/I(H35Cl+) vs. J′ derived from Q rotational lines of REMPI spectra due to two-photon resonance excitations to the Rydberg states E 1Σ+ (v′ = 1) (a) and E 1Σ+ (v′ = 0) (b). (c) H79Br: Relative ion signal intensities, I(79Br+)/I(H79Br+) vs. J′ derived from Q rotational lines of REMPI spectra due to two-photon resonance excitations to the Rydberg state E 1Σ+ (v′ = 0). Gray columns are experimental values. The black and white columns are calculated values for the contributions due to the interactions of the E(v′) states with the lower energy V states (V L ) and the higher energy V states (V H ), respectively.

Image of FIG. 5.
FIG. 5.

HBr: Rotational line-widths vs J′ derived from Q lines of H79Br REMPI spectra for V 1Σ+(v′ = m + 5) (top), E 1Σ+(v′ = 0) (middle) and V 1Σ+(v′ = m + 4) (bottom).

Image of FIG. 6.
FIG. 6.

Semischematic figure, showing the HBr energetics, state interactions and energy transfers of relevance to the data presented (see text). Electrostatic, rotational and spin-orbit couplings are marked E, JL and SO, respectively. Red boxes represent the ion-pair states. Blue and purple boxes are Rydberg states and black curves are repulsive states. The blue box with solid lines represents a manifold of many Rydberg states, which couple with the ion-pair states. The blue boxes with broken lines are gateway states with respect to predissociation of other states. Relative importance of couplings and transfers are indicated by different boldness of arrows and broken lines as well as by use of brackets or not. The colored arrows indicate the major paths towards predissociation for the V and E states.

Tables

Generic image for table
Table I.

ΔE J ′ relevant to off-resonance interactions between E 1Σ+(v′ = 1) and V 1Σ+ (v′ = 14,15) states (H35Cl) (left), E 1Σ+(v′ = 0) and V 1Σ+ (v′ = 10,11) states (H35Cl) (middle) and E 1Σ+(v′ = 0) and V 1Σ+ (v′ = m + 4,m + 5) states (HBr) (right).

Generic image for table
Table II.

Parameters used in analysis if relative ion signal intensities I( i X+)/I(H i X+) ( i X = 35Cl, 79Br) as a function of J′ for (2 + n) REMPI of E 1Σ+(v′) Rydberg states (see definitions in text).

Generic image for table
Table III.

Spectroscopic parameters derived from direct analysis of observed spectral lines (Obs.) and from deperturbation analysis (Dep.) (see text), (a) for E 1 Σ+(v′ = 1), V 1Σ+(v′ = 14, 15) (H35Cl) by using interaction strengths W L = 124 cm−1 and W H = 126 cm−1. Observed values are from this work (above) and from Ref. 3 (below). (b) For E 1Σ+(v′ = 0), V 1Σ+(v′ = 10, 11) (H35Cl) by using interaction strengths W L = 191 cm−1 and W H = 194 cm−1. Observed values are from this work and from Ref. 3 (below). (c) For E 1Σ+(v′ = 0), V 1Σ+(v′ = m + 4, m + 5) (H79Br) by using interaction strengths W L = 57 cm−1 and W H = 97 cm−1. Observed values are from this work (top) and from Refs. 8 (middle) and 2 (bottom).

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/content/aip/journal/jcp/138/4/10.1063/1.4776260
2013-01-25
2014-04-24
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Scitation: Photofragmentations, state interactions, and energetics of Rydberg and ion-pair states: Resonance enhanced multiphoton ionization via E and V (B) states of HCl and HBr
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/4/10.1063/1.4776260
10.1063/1.4776260
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