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Photoisomerization of acetone via Rydberg excitation

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Abstract

Acetone photochemistry upon excitation by vacuum ultraviolet (VUV) radiation of photon energy 7.75 eV has been investigated under a cryogenic condition of an argon matrix (8 K) and also by shining the molecule seeded in an effusive beam of argon prior to matrix deposition on a pre-cooled KBr window, where the photo-products get trapped in the argon matrix. Product analysis by infrared spectroscopy reveals appearance of the characteristic enolic O-H stretching fundamental at 3622 cm-1 and other bands in the infrared fingerprint region, including C=C stretching only in the gas phase. The findings reveal the opening of a new isomerization reaction channel of acetone over the popular Norrish type-I α-CC bond cleavage upon VUV excitation to high-lying Rydberg states.

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SYNOPSIS Photochemical transformation of acetone upon excitation by vacuum ultraviolet radiation of photon energy 7.75 eV is reported under a cryogenic condition of an argon matrix (8 K). Infrared spectroscopic analysis of the products reveals that acetone isomerizes to the enolic form, 1-propene-2-ol, upon excitation to the high-lying Rydberg states.

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References

  1. McDiamrmid R and Sabljic A 1988 Experimental assignments of the 3p Rydberg states of acetone J. Chem. Phys. 89 6086

    Article  ADS  Google Scholar 

  2. Diau EW-G, Kötting C, Sølling T I and Zewail A H 2002 Femtochemistry of Norrish Type-I Reactions:III. Highly Excited Ketones-Theoretical ChemPhysChem 3 57

    Article  CAS  PubMed  Google Scholar 

  3. Merchan M, Roos B O, McDiarmid R and Xing X 1996 A Combined Theoretical and Experimental Determination of the Electronic Spectrum of Acetone J. Chem. Phys. 104 1791

    Article  CAS  ADS  Google Scholar 

  4. Nobre M, Fernandes A, Ferreira da Silva F, Antunes R, Almeida D, Kokhan V et al. 2008 The VUV Electronic Spectroscopy of Acetone Studied by Synchrotron Radiation Phys. Chem. Chem. Phys. 10 550

    Article  CAS  PubMed  Google Scholar 

  5. Huebner R H, Celotta R J, Mielczarek S R and Kuyatt C E 1973 Electron energy loss spectroscopy of acetone vapor J. Chem. Phys. 59 5434

    Article  CAS  ADS  Google Scholar 

  6. Walzl K N, Koerting C F and Kuppermann A 1987 Electron impact spectroscopy of acetaldehyde J. Chem. Phys. 87 3796

    Article  CAS  ADS  Google Scholar 

  7. Rocha A B and Bielschowsky C E 2001 Intensity of the n→π* symmetry-forbidden electronic transition in acetone by direct vibronic coupling mechanism Chem. Phys. Lett. 337 331

    Article  CAS  ADS  Google Scholar 

  8. Wiedmann R T, Goodman L and White M G 1998 Two-color zero kinetic energy–pulsed field ionization spectroscopy of the acetone n-radical cation: the a2 torsional vibration Chem. Phys. Lett. 293 391

    Article  CAS  ADS  Google Scholar 

  9. Haas Y 2004 Photochemical α-cleavage of ketones: revisiting acetone Photochem. Photobiol. Sci. 3 6

    Article  CAS  PubMed  Google Scholar 

  10. Zuckermann H, Schmitz B and Haas Y 1988 Dissociation Energy of an Isolated Triplet Acetone Molecule J. Phys. Chem. 92 4835

    Article  CAS  Google Scholar 

  11. Hüter O and Temps F 2016 Ultrafast α−CC bond cleavage of acetone upon excitation to 3p and 3d Rydberg states by femtosecond time-resolved photoelectron imaging J. Chem. Phys. 145 214312

    Article  PubMed  ADS  Google Scholar 

  12. Bell R and Smith P 1966 The Enol Content and Acidity of Cyclopentanone, Cyclohexanone, and Acetone in Aqueous Solution J. Chem. Soc. B 241

  13. Shaw M F, Sztáray B, Whalley L K, Heard D E, Millet D B, Jordan M J T et al. 2018 Photo-tautomerization of acetaldehyde as a photochemical source of formic acid in the troposphere Nat. Commun. 9 2584

    Article  PubMed  PubMed Central  ADS  Google Scholar 

  14. Matsuda Y, Hoki K, Maeda S, Hanaue K, Ohta K, Morokuma K et al. 2012 Experimental and theoretical investigations of isomerization reactions of ionized acetone and its dimer Phys. Chem. Chem. Phys. 14 712

    Article  CAS  PubMed  Google Scholar 

  15. Zhang X K, Parnis J M, Lewars E G and March R E 1997 FTIR spectroscopic investigation of matrix-isolated isomerization and decomposition products of ionized acetone: generation and characterization of 1-propen-2-ol Can. J. Chem. 75 276

    Article  CAS  Google Scholar 

  16. McMillan G R, Calvert J G and Pitts J N Jr 1964 Detection and Lifetime of Enol-Acetone in the Photolysis of 2-Pentanone Vapor J. Am. Chem. Soc. 86 3602

  17. Bhattacharya I, Banerjee P, Sadhukhan J and Chakraborty T 2019 Modulations of νO–H and νC=O Stretching Frequencies of Difluoroacetic Acid with Internal Rotation of CHF2 Rotor: A Combined Vapor Phase and Matrix Isolation Infrared Spectroscopy Study J. Phys. Chem. A 123 2771

    Article  CAS  PubMed  Google Scholar 

  18. Banerjee P, Bhattacharya I and Chakraborty T 2016 Matrix Isolation Infrared Spectroscopy of an O-H···π Hydrogen Bonded Complex between Formic Acid and Benzene J. Phys. Chem. A 120 3731.

  19. Lofthus A and Krupenie P H 1977 The Spectrum of Molecular Nitrogen J. Phys. Chem. Ref. Data 6 113

    Article  CAS  ADS  Google Scholar 

  20. Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Scalmani G, Barone V, Mennucci B, Petersson G A, Nakatsuji H, Caricato M, Li X, Hratchian H P, Izmaylov A F, Bloino J, Zheng G, Sonnenberg J L, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr. J A, Peralta J E, Ogliaro F, Bearpark M, Heyd J J, Brothers E, Kudin K N, Staroverov V N, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant J C, Iyengar S S, Tomasi J, Cossi M, Rega N, Millam J M, Klene M, Knox J E, Cross J B, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J W, Martin R L, Morokuma K, Zakrzewski V G, Voth G A, Salvador P, Dannenberg J J, Dapprich S, Daniels A D, Farkas O, Foresman J B, Ortiz J V, Cioslowski J and Fox D J 2013 Gaussian 09, Revision D.01

  21. Zhang X K, Lewars E G, March R E and Parnis J M 1993 Vibrational Spectrum of the Acetone-Water Complex: A Matrix Isolation FTIR and Theoretical Study J. Phys. Chem. 97 4320

    Article  CAS  Google Scholar 

  22. Jiang X, Liu S, Tsona NT, Tang S, Ding L, Zhao H and Du L 2017 Matrix Isolation FTIR Study of Hydrogen-Bonded Complexes of Methanol with Heterocyclic Organic Compounds RSC Adv. 7 2503

    Article  CAS  ADS  Google Scholar 

  23. Barnes A J and Hallam H E 1970 Infra-red Cryogenic Studies Part 5.-Ethanol and Ethanol-d in Argon Matrices Trans Faraday Soc. 66 1932

    Article  CAS  Google Scholar 

  24. Coussan S, Bouteiller Y, Perchard J P and Zheng W Q 1998 Rotational Isomerism of Ethanol and Matrix Isolation Infrared Spectroscopy J. Phys. Chem. A 102 5789

    Article  CAS  Google Scholar 

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Acknowledgements

The authors acknowledge the financial support from the Ministry of Earth Sciences (MoES/16/13/2018) and the Indian Association for the Cultivation of Science.

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Authors and Affiliations

  1. School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & B Raja S C Mullick Road, Jadavpur, Kolkata, 700032, India

    Piyali Chatterjee & Tapas Chakraborty

  2. Indian Oil Corporation Limited, Regional Laboratory, Korukkupet, Chennai, 600021, India

    Monoj Samanta

  3. Department of Chemical and Biological Sciences, S. N. Bose National Centre for Basic Sciences, Salt Lake, JD Block, Sector III, Bidhannagar, Kolkata, 700106, India

    Indrani Bhattacharya & Koushik Mondal

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  1. Monoj Samanta
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  2. Indrani Bhattacharya
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  3. Piyali Chatterjee
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  5. Tapas Chakraborty
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Correspondence to Tapas Chakraborty.

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Dedicated to Prof. S.P. Bhattacharyya on the occasion of his 75th birthday.

Special Issue on Interplay of Structure and Dynamics in Reaction Pathways, Chemical Reactivity and Biological Systems

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Samanta, M., Bhattacharya, I., Chatterjee, P. et al. Photoisomerization of acetone via Rydberg excitation. J Chem Sci 135, 49 (2023). https://doi.org/10.1007/s12039-023-02155-4

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  • DOI: https://doi.org/10.1007/s12039-023-02155-4

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