(2+n) REMPI of acetylene: Gerade Rydberg states and photorupture channels

Matthíasson, Kristján; Wang, Huasheng; Kvaran, Ágúst

doi:10.1016/j.cplett.2008.04.104

Cited by 8 publications

(20 citation statements)

References 31 publications

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“…Rotational line-widths of the E(v )(v = 0,1) and V (v ) (v = 10,11,14, and 15) states REMPI spectra for H i Cl are all close to our detection limit of about 0.3-0.4 cm −1 which suggests that predissociation is not of major importance for these states 18,27 (see Figs. 1(a) and 1(b)).…”

Section: Line-widthssupporting

confidence: 67%

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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

Long

Wang

Kvaran

2013

The Journal of Chemical Physics

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(2 + n) resonance enhanced multiphoton ionization mass spectra for resonance excitations to diabatic E(1)Σ(+) (v') Rydberg and V (1)Σ(+) (v') ion-pair states (adiabatic B(1)Σ(+)(v') states) of H(i)Cl (i = 35,37) and H(i)Br (i = 79,81) were recorded as a function of excitation wavenumber (two-dimensional REMPI). Simulation analyses of ion signal intensities, deperturbation analysis of line shifts and interpretations of line-widths are used to derive qualitative and quantitative information concerning the energetics of the states, off-resonance interactions between the E states and V states, closest in energy as well as on predissociation channels. Spectroscopic parameters for the E(1)Σ(+) (v')(v' = 1) for H(35)Cl and v' = 0 for H(79)Br states, interaction strengths for E - V state interactions and parameters relevant to dissociation of the E states are derived. An overall interaction and dynamical scheme, to describe the observations for HBr, is proposed.

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Section: Line-widthssupporting

confidence: 67%

“…This agrees with the derivation of γ ≈ 0 values, hence negligible dissociation, for the E states according to the intensity ratio analysis mentioned before. The lifetime (τ ), being inversely proportional to the line-width as 18,27,28 τ (ps) = 5.3/ (cm −1 )…”

Section: Line-widthsmentioning

confidence: 99%

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

Long

Wang

Kvaran

2013

The Journal of Chemical Physics

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“…[25][26][27][28][29][30][31][32][33][34] It has been pointed out that analogous effects are to be found for methyl bromide. 18,19 In this paper we report a two-dimensional (2+n) REMPI experiment analogous to those presented before for acetylene 35 and HCl, 25,34,36 which helps elucidate the discrepancy concerning the VUV spectroscopy of methyl bromide, and which also yields evidence for new photodissociation channels via Rydberg states. First, it allows us to assign several new vibronic bands and to confirm the assignment by Causley and Russel based on single photon absorption data.…”

Section: Introductionmentioning

confidence: 88%

Two-Dimensional (2+n) REMPI of CH₃Br: Photodissociation Channels via Rydberg States

et al. 2010

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(2+n) resonance enhanced multiphoton ionization (REMPI) spectra of CH(3)Br for the masses H(+), CH(m)(+), (i)Br(+), H(i)Br(+), and CH(m)(i)Br(+) (m = 0-3; i = 79, 81) have been recorded in the 66 000-81 000 cm(-1) resonance energy range. Signals due to resonance transitions from the zero vibrational energy level of the ground state CH(3)Br to a number of Rydberg states [Ω(c)]nl;ω (Ω(c) = 3/2, 1/2; ω = 0, 2; l = 1(p), 2(d)) and various vibrational states were identified. C((3)P) and C*((1)D) atom and HBr intermediate production, detected by (2+1) REMPI, most probably is due to photodissociation of CH(3)Br via two-photon excitations to Rydberg states followed by an unusual breaking of four bonds and formation of two bonds to give the fragments H(2) + C/C* + HBr prior to ionization. This observation is supported by REMPI observations as well as potential energy surface (PES) ab initio calculations. Bromine atom production by photodissociation channels via two-photon excitation to Rydberg states is identified by detecting bromine atom (2+1) REMPI.

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“…Figure 6 shows rotational line-widths ( ) as a function of J . Lower limit lifetimes (τ ) derived from 6,30 τ (ps) = 5.3/ (cm −1 )…”

Section: Line-widths and Fragmentations Vs State Interactionsmentioning

confidence: 99%

Photofragmentations, state interactions, and energetics of Rydberg and ion-pair states: Two-dimensional resonance enhanced multiphoton ionization of HBr via singlet-, triplet-, Ω = 0 and 2 states

Long

Hróðmarsson

Wang

et al. 2012

The Journal of Chemical Physics

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Mass spectra were recorded for one-colour resonance enhanced multiphoton ionization (REMPI) of H(i)Br (i = 79, 81) for the two-photon resonance excitation region 79,040-80,300 cm(-1) to obtain two-dimensional REMPI data. The data were analysed in terms of rotational line positions, intensities, and line-widths. Quantitative analysis of the data relevant to near-resonance interactions between the F(1)Δ(2)(v' = 1) and V(1)Σ(+)(v' = m + 7) states gives interaction strengths, fractional state mixing, and parameters relevant to dissociation of the F state. Qualitative analysis further reveals the nature of state interactions between ion-pair states and the E(1)Σ(+) (v' = 1) and H(1)Σ(+)(v' = 0) Rydberg states in terms of relative strengths and J' dependences. Large variety in line-widths, depending on electronic states and J' quantum numbers, is indicative of number of different predissociation channels. The relationship between line-widths, line-shifts, and signal intensities reveals dissociation mechanisms involving ion-pair to Rydberg state interactions prior to direct or indirect predissociations of Rydberg states. Quantum interference effects are found to be important. Moreover, observed bromine atom (2 + 1) REMPI signals support the importance of Rydberg state predissociation channels. A band system, not previously observed in REMPI, was observed and assigned to the k(3)Π(0)(v' = 0) ←← X transition with band origin 80,038 cm(-1) and rotational parameter B(v('))=7.238 cm(-1).

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(2+n) REMPI of acetylene: Gerade Rydberg states and photorupture channels

Cited by 8 publications

References 31 publications

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

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

Two-Dimensional (2+n) REMPI of CH₃Br: Photodissociation Channels via Rydberg States

Photofragmentations, state interactions, and energetics of Rydberg and ion-pair states: Two-dimensional resonance enhanced multiphoton ionization of HBr via singlet-, triplet-, Ω = 0 and 2 states

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(2+n) REMPI of acetylene: Gerade Rydberg states and photorupture channels

Cited by 8 publications

References 31 publications

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

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

Two-Dimensional (2+n) REMPI of CH3Br: Photodissociation Channels via Rydberg States

Photofragmentations, state interactions, and energetics of Rydberg and ion-pair states: Two-dimensional resonance enhanced multiphoton ionization of HBr via singlet-, triplet-, Ω = 0 and 2 states

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Two-Dimensional (2+n) REMPI of CH₃Br: Photodissociation Channels via Rydberg States