Molecular predissociation dynamics revealed through multiphoton ionisation spectroscopy. III. New 1A2 and 1B1 rydberg states in H2S D2S

Ashfold, Michael N. R.; Bayley, J. M.; Dixon, Ronald; Prince, Jd

doi:10.1016/0301-0104(85)80142-7

Cited by 22 publications

(4 citation statements)

References 43 publications

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“…The 2 + 1 and 3 + 1 REMPI studies of H 2 S and D 2 S confirmed the origin of the 2 1 A 2 (4b 2 ← 2b 1 ) state at 7.89 eV, 65,66 near coincident with a weak feature in the one photon spectrum 44 and in excellent accord with the current theoretical prediction (Table 1). As Table S1† shows, the 2 1 A 2 – X̃ 1 A 1 transition is one-photon forbidden in the C 2v group, but it could gain some transition strength by coupling with near resonant states of 1 B 1 symmetry.…”

Section: Resultssupporting

confidence: 84%

The vibronic state dependent predissociation of H₂S: determination of all fragmentation processes

et al. 2023

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Section: Resultssupporting

confidence: 84%

The vibronic state dependent predissociation of H₂S: determination of all fragmentation processes

et al. 2023

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“…Several of these Rydberg states are sufficiently long-lived (i.e., predissociate sufficiently slowly) that their spectra show resolved rotational fine structure. 28,29,31,32 Table 1 shows threshold energies for the various spinallowed fragmentation channels of H 2 S molecules at the photolysis wavelength of particular interest in the present work. The threshold energies for channels I−IV are also included in Figure 1, along with the vibrational energies of the SH products.…”

Section: Introductionmentioning

confidence: 99%

“…This causes a negligible change in equilibrium geometry, and the associated Franck–Condon factors thus ensure that the absorption to each of these Rydberg states is dominated by the origin band (i.e., the v ′ = 0 ← v ″ = 0 transition). Several of these Rydberg states are sufficiently long-lived (i.e., predissociate sufficiently slowly) that their spectra show resolved rotational fine structure. ,,, …”

Section: Introductionmentioning

confidence: 99%

Unraveling the Rich Fragmentation Dynamics Associated with S–H Bond Fission Following Photoexcitation of H₂S at Wavelengths ∼129.1 nm

Luo,

Wu,

Yang

et al. 2024

J. Phys. Chem. A

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H 2 S is being detected in the atmospheres of ever more interstellar bodies, and photolysis is an important mechanism by which it is processed. Here, we report H Rydberg atom time-of-flight measurements following the excitation of H 2 S molecules to selected rotational (J KaKc ′) levels of the 1 B 1 Rydberg state associated with the strong absorption feature at wavelengths of λ ∼ 129.1 nm. Analysis of the total kinetic energy release spectra derived from these data reveals that all levels predissociate to yield H atoms in conjunction with both SH(A) and SH(X) partners and that the primary SH(A)/SH(X) product branching ratio increases steeply with ⟨J b 2 ⟩, the square of the rotational angular momentum about the b-inertial axis in the excited state. These products arise via competing homogeneous (vibronic) and heterogeneous (Coriolis-induced) predissociation pathways that involve coupling to dissociative potential energy surfaces (PES(s)) of, respectively, 1 A″ and 1 A′ symmetries. The present data also show H + SH(A) product formation when exciting the J KaKc ′ = 0 00 and 1 11 levels, for which ⟨J b 2 ⟩ = 0 and Coriolis coupling to the 1 A′ PES(s) is symmetry forbidden, implying the operation of another, hitherto unrecognized, route to forming H + SH(A) products following excitation of H 2 S at energies above ∼9 eV. These data can be expected to stimulate future ab initio molecular dynamic studies that test, refine, and define the currently inferred predissociation pathways available to photoexcited H 2 S molecules.

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“…Hydrogen sulfide cation (H 2 S + ) is a key component and an essential partaker in the synthesis of sulfur-containing molecules in various environments. − As a prototype of bent triatomic ions, H 2 S + shows nonadiabatic couplings between the excited states. − Furthermore, the photodissociation of hydrogen sulfide cations H 2 S + (X 2 B 1 ) → H 2 (X 1 Σ g + )+S + ( 4 S) is a spin-forbidden process and can only take place via nonadiabatic couplings . Over the past decades, much attention has been made to experimental and theoretical studies of H 2 S + in an effort to clarify the photodissociation dynamics. − …”

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confidence: 99%

Observation of Competitive Nonadiabatic Photodissociation Dynamics of H₂S⁺ Cations

Luan

Tan

et al. 2022

J. Phys. Chem. Lett.

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A comprehensive understanding of dissociation mechanisms is of fundamental importance in the photochemistry of small molecules. Here, we investigated the detailed photodissociation dynamics of H2S+ near 337 nm by using the velocity map ion imaging technique together with the theoretical characterizations by developing global full-dimensional potential energy surfaces (PESs). Rotational state resolved images were acquired for the S+(4S) + H2 product channel. Significant changes in product total kinetic energy release distributions and angular distributions have been observed within a small excitation photon energy range of 5 wavenumbers. Analysis based on the full-dimensional PESs reveals that two nonadiabatic pathways determined by the transition state connecting two minima on the 12A′ state are responsible for the dramatic variation of observed product distributions. The current study has directly witnessed the competitive photodissociation mechanisms controlled by a critical energy point on the PES, thereby providing in-depth insight into the nonadiabatic dynamics in photochemistry.

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Molecular predissociation dynamics revealed through multiphoton ionisation spectroscopy. III. New 1A2 and 1B1 rydberg states in H2S D2S

Cited by 22 publications

References 43 publications

The vibronic state dependent predissociation of H₂S: determination of all fragmentation processes

The vibronic state dependent predissociation of H₂S: determination of all fragmentation processes

Unraveling the Rich Fragmentation Dynamics Associated with S–H Bond Fission Following Photoexcitation of H₂S at Wavelengths ∼129.1 nm

Observation of Competitive Nonadiabatic Photodissociation Dynamics of H₂S⁺ Cations

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Molecular predissociation dynamics revealed through multiphoton ionisation spectroscopy. III. New 1A2 and 1B1 rydberg states in H2S D2S

Cited by 22 publications

References 43 publications

The vibronic state dependent predissociation of H2S: determination of all fragmentation processes

The vibronic state dependent predissociation of H2S: determination of all fragmentation processes

Unraveling the Rich Fragmentation Dynamics Associated with S–H Bond Fission Following Photoexcitation of H2S at Wavelengths ∼129.1 nm

Observation of Competitive Nonadiabatic Photodissociation Dynamics of H2S+ Cations

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The vibronic state dependent predissociation of H₂S: determination of all fragmentation processes

The vibronic state dependent predissociation of H₂S: determination of all fragmentation processes

Unraveling the Rich Fragmentation Dynamics Associated with S–H Bond Fission Following Photoexcitation of H₂S at Wavelengths ∼129.1 nm

Observation of Competitive Nonadiabatic Photodissociation Dynamics of H₂S⁺ Cations