Investigating the Rydberg states and photodissociation dynamics of Kr2 using velocity map imaging

Research output: Contribution to journalArticleResearchpeer review

Authors

  • Cailum M.K. Stienstra
  • Neville J.A. Coughlan
  • Alexander Haack
  • Patrick J.J. Carr
  • Jeff Crouse
  • Joshua Featherstone
  • W. Scott Hopkins

External Research Organisations

  • University of Waterloo
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Details

Original languageEnglish
Pages (from-to)505-515
Number of pages11
JournalCanadian journal of chemistry
Volume101
Issue number8
Publication statusPublished - Aug 2023
Externally publishedYes

Abstract

Although the krypton dimer, Kr2, is a prototypical weakly bound van der Waals complex in its ground electronic state, the excited states of Kr2 exhibit many and various interactions. Resonance-enhanced multiphoton ionization and velocity map imaging provide an avenue to explore the electronic structure and photofragmentation dynamics of Kr2 in the vacuum ultraviolet region. By monitoring photofragmentation product channels and recoil anisotropy distributions, one can gain insights into excited state symmetries and lifetimes, which can aid in interpreting spectroscopy. Here, we study the spectroscopy and photodissociation dynamics of Kr2 in the 91 000–94 500 cm−1 region. We record and assign photofragment product channels for 32 vibronic bands corresponding to seven electronic transitions. We also identify two previously unobserved vibronic band systems, which we assign as the Kr2 5p [5/2]3 1g ← X0+gand 5p [3/2]20+g←X0+g transitions. Velocity map images show photofragments arising from predissociation of the neutral Rydberg states and from dissociative photoionization at the n > 2 photon level. We also observe variation in branching ratios between the predissociative and dissociative photoionization channels depending on the lifetime of the intermediate; longer lived states favour higher dissociative photoionization yields and exhibit β6 anisotropy parameters for predissociation product channels, indicating “rotational smearing” of the product angular distributions.

Keywords

    krypton dimer, photofragment imaging, REMPI spectroscopy, Rydberg states, time-of-flight spectrometry, VMI

ASJC Scopus subject areas

Cite this

Investigating the Rydberg states and photodissociation dynamics of Kr2 using velocity map imaging. / Stienstra, Cailum M.K.; Coughlan, Neville J.A.; Haack, Alexander et al.
In: Canadian journal of chemistry, Vol. 101, No. 8, 08.2023, p. 505-515.

Research output: Contribution to journalArticleResearchpeer review

Stienstra, CMK, Coughlan, NJA, Haack, A, Carr, PJJ, Crouse, J, Featherstone, J & Scott Hopkins, W 2023, 'Investigating the Rydberg states and photodissociation dynamics of Kr2 using velocity map imaging', Canadian journal of chemistry, vol. 101, no. 8, pp. 505-515. https://doi.org/10.1139/cjc-2022-0283
Stienstra, C. M. K., Coughlan, N. J. A., Haack, A., Carr, P. J. J., Crouse, J., Featherstone, J., & Scott Hopkins, W. (2023). Investigating the Rydberg states and photodissociation dynamics of Kr2 using velocity map imaging. Canadian journal of chemistry, 101(8), 505-515. https://doi.org/10.1139/cjc-2022-0283
Stienstra CMK, Coughlan NJA, Haack A, Carr PJJ, Crouse J, Featherstone J et al. Investigating the Rydberg states and photodissociation dynamics of Kr2 using velocity map imaging. Canadian journal of chemistry. 2023 Aug;101(8):505-515. doi: 10.1139/cjc-2022-0283
Stienstra, Cailum M.K. ; Coughlan, Neville J.A. ; Haack, Alexander et al. / Investigating the Rydberg states and photodissociation dynamics of Kr2 using velocity map imaging. In: Canadian journal of chemistry. 2023 ; Vol. 101, No. 8. pp. 505-515.
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title = "Investigating the Rydberg states and photodissociation dynamics of Kr2 using velocity map imaging",
abstract = "Although the krypton dimer, Kr2, is a prototypical weakly bound van der Waals complex in its ground electronic state, the excited states of Kr2 exhibit many and various interactions. Resonance-enhanced multiphoton ionization and velocity map imaging provide an avenue to explore the electronic structure and photofragmentation dynamics of Kr2 in the vacuum ultraviolet region. By monitoring photofragmentation product channels and recoil anisotropy distributions, one can gain insights into excited state symmetries and lifetimes, which can aid in interpreting spectroscopy. Here, we study the spectroscopy and photodissociation dynamics of Kr2 in the 91 000–94 500 cm−1 region. We record and assign photofragment product channels for 32 vibronic bands corresponding to seven electronic transitions. We also identify two previously unobserved vibronic band systems, which we assign as the Kr2 5p [5/2]3 1g ← X0+gand 5p [3/2]20+g←X0+g transitions. Velocity map images show photofragments arising from predissociation of the neutral Rydberg states and from dissociative photoionization at the n > 2 photon level. We also observe variation in branching ratios between the predissociative and dissociative photoionization channels depending on the lifetime of the intermediate; longer lived states favour higher dissociative photoionization yields and exhibit β6 anisotropy parameters for predissociation product channels, indicating “rotational smearing” of the product angular distributions.",
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note = "Funding Information: WSH acknowledges funding from the Canadian Foundation for Innovation (CFI), Ontario Research Fund (ORF), and Natural Sciences and Engineering Research Council (NSERC) of Canada in the form of a Discovery Grant. CMKS acknowledges financial support from NSERC in the form of a Canadian Graduate Scholarship. NJAC acknowledges financial support from the NSERC Banting postdoctoral fellowship program. AH gratefully acknowledges this work being funded by the Deutsche Forschungsgemeinschaft (DFG; German Research Foundation; 449651261). Canadian Foundation for Innovation, Ontario Research Fund, Natural Sciences and Engineering Research Council of Canada, Deutsche Forschungsgemeinschaft (DFG; German Research Foundation). ",
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Download

TY - JOUR

T1 - Investigating the Rydberg states and photodissociation dynamics of Kr2 using velocity map imaging

AU - Stienstra, Cailum M.K.

AU - Coughlan, Neville J.A.

AU - Haack, Alexander

AU - Carr, Patrick J.J.

AU - Crouse, Jeff

AU - Featherstone, Joshua

AU - Scott Hopkins, W.

N1 - Funding Information: WSH acknowledges funding from the Canadian Foundation for Innovation (CFI), Ontario Research Fund (ORF), and Natural Sciences and Engineering Research Council (NSERC) of Canada in the form of a Discovery Grant. CMKS acknowledges financial support from NSERC in the form of a Canadian Graduate Scholarship. NJAC acknowledges financial support from the NSERC Banting postdoctoral fellowship program. AH gratefully acknowledges this work being funded by the Deutsche Forschungsgemeinschaft (DFG; German Research Foundation; 449651261). Canadian Foundation for Innovation, Ontario Research Fund, Natural Sciences and Engineering Research Council of Canada, Deutsche Forschungsgemeinschaft (DFG; German Research Foundation).

PY - 2023/8

Y1 - 2023/8

N2 - Although the krypton dimer, Kr2, is a prototypical weakly bound van der Waals complex in its ground electronic state, the excited states of Kr2 exhibit many and various interactions. Resonance-enhanced multiphoton ionization and velocity map imaging provide an avenue to explore the electronic structure and photofragmentation dynamics of Kr2 in the vacuum ultraviolet region. By monitoring photofragmentation product channels and recoil anisotropy distributions, one can gain insights into excited state symmetries and lifetimes, which can aid in interpreting spectroscopy. Here, we study the spectroscopy and photodissociation dynamics of Kr2 in the 91 000–94 500 cm−1 region. We record and assign photofragment product channels for 32 vibronic bands corresponding to seven electronic transitions. We also identify two previously unobserved vibronic band systems, which we assign as the Kr2 5p [5/2]3 1g ← X0+gand 5p [3/2]20+g←X0+g transitions. Velocity map images show photofragments arising from predissociation of the neutral Rydberg states and from dissociative photoionization at the n > 2 photon level. We also observe variation in branching ratios between the predissociative and dissociative photoionization channels depending on the lifetime of the intermediate; longer lived states favour higher dissociative photoionization yields and exhibit β6 anisotropy parameters for predissociation product channels, indicating “rotational smearing” of the product angular distributions.

AB - Although the krypton dimer, Kr2, is a prototypical weakly bound van der Waals complex in its ground electronic state, the excited states of Kr2 exhibit many and various interactions. Resonance-enhanced multiphoton ionization and velocity map imaging provide an avenue to explore the electronic structure and photofragmentation dynamics of Kr2 in the vacuum ultraviolet region. By monitoring photofragmentation product channels and recoil anisotropy distributions, one can gain insights into excited state symmetries and lifetimes, which can aid in interpreting spectroscopy. Here, we study the spectroscopy and photodissociation dynamics of Kr2 in the 91 000–94 500 cm−1 region. We record and assign photofragment product channels for 32 vibronic bands corresponding to seven electronic transitions. We also identify two previously unobserved vibronic band systems, which we assign as the Kr2 5p [5/2]3 1g ← X0+gand 5p [3/2]20+g←X0+g transitions. Velocity map images show photofragments arising from predissociation of the neutral Rydberg states and from dissociative photoionization at the n > 2 photon level. We also observe variation in branching ratios between the predissociative and dissociative photoionization channels depending on the lifetime of the intermediate; longer lived states favour higher dissociative photoionization yields and exhibit β6 anisotropy parameters for predissociation product channels, indicating “rotational smearing” of the product angular distributions.

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KW - photofragment imaging

KW - REMPI spectroscopy

KW - Rydberg states

KW - time-of-flight spectrometry

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