Internal conversion versus intersystem crossing: What drives the gas phase dynamics of cyclic α,β-enones?

Journal of Physical Chemistry A

Volumn 118, Issue 12, 2014, Pages 2279-2287

  Schalk, Oliver ^a,b,c   Schuurman, Michael S ^c   Wu, Guorong ^c,d,e   Lang, Peter ^b   Mucke, Melanie ^f   Feifel, Raimund ^f   Stolow, Albert ^c  

^a ALBANOVA UNIVERSITY CENTER   (Sweden)

^b UNIVERSITY OF MUNICH   (Germany)

^c NATIONAL RESEARCH COUNCIL CANADA   (Canada)

^d DALIAN INSTITUTE OF CHEMICAL PHYSICS   (China)

^e UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA   (China)

^f UPPSALA UNIVERSITY   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYLATION; PHOTOELECTRON SPECTROSCOPY; QUANTUM CHEMISTRY; QUANTUM YIELD;

AB INITIO COMPUTATIONS; CONICAL INTERSECTION; INTER-SYSTEM CROSSINGS; INTERNAL CONVERSIONS; NON-RADIATIVE RELAXATION; SINGLET AND TRIPLET STATE; SINGLET GROUND STATE; TIME-RESOLVED PHOTOELECTRON SPECTROSCOPY;

QUANTUM THEORY;

3-BUTEN-2-ONE; ALKANONE; CYCLOALKANE DERIVATIVE; GAS; KETONE;

CHEMICAL STRUCTURE; CHEMISTRY; GAS; KINETICS; PLIABILITY; QUANTUM THEORY; VIBRATION; X RAY PHOTOELECTRON SPECTROSCOPY;

BUTANONES; CYCLOPARAFFINS; GASES; KETONES; KINETICS; MOLECULAR STRUCTURE; PHOTOELECTRON SPECTROSCOPY; PLIABILITY; QUANTUM THEORY; VIBRATION;

EID: 84897396214     PISSN: 10895639     EISSN: 15205215     Source Type: Journal    
DOI: 10.1021/jp4124937     Document Type: Article

References (47)

1. Richard, R.; Sauvage, P.; Wan, C. S. K.; Weedon, A. C.; Wong, D. F. Photochemical Enolization of Acyclic β-alkyl-α,β-unsaturated Ketones J. Org. Chem. 1986, 51, 62-67
2. Wolff, S.; Schreiber, W. L.; Smith, A. B., II; Agosta, W. C. Photochemistry of Cyclopentenones. Hydrogen Abstraction by the β-Carbon Atom J. Am. Chem. Soc. 1972, 94, 7797-7806
3. Su, M.-D. The Role of Spin-Orbit Coupling and Symmetry in Photochemical Rearrangements of α,β-Unsaturated Cyclic Ketones Chem. Phys. 1996, 205, 277-308
4. Carey, F. A.; Sundberg, R. J. Organische Chemie; Wiley VCH: Weinheim, 1995; Vol. 1.
5. Fang, W.-H. A CASSCF Study on Photodissociation of Acrolein in the Gas Phase J. Am. Chem. Soc. 1999, 121, 8376-8384
6. Aquilante, F.; Barone, V.; Roos, O. B. A Theoretical Investigation of Valence and Rydberg Electronic States of Acrolein J. Chem. Phys. 2003, 119, 12323-12334
7. Beljonne, D.; Shuai, Z.; Pourtois, G.; Bredas, J. L. Spin-Orbit Coupling and Intersystem Crossing in Conjugated Polymers: A Configuration Interaction Description J. Phys. Chem. A 2001, 105, 3899-3907
8. El-Sayed, M. A. Spin-Orbit Coupling and the Radiationless Processes in Nitrogen Heterocyclics J. Chem. Phys. 1963, 38, 2834-2838
9. Reguero, M.; Olivucci, M.; Bernardi, F.; Robb, M. A. Excited-State Potential Surface Crossings in Acrolein: A Model for Understanding the Photochemistry and Photophysics of α,β-Enones J. Am. Chem. Soc. 1994, 116, 2103-2114
10. 0 Intersections and Triplet Lifetimes of Cyclic α,β-Enones J. Org. Chem. 2001, 66, 8811-8814
11. Wu, W.; Yang, C.; Zhao, H.; Liu, K.; Su, H. Photodissociation and Photoisomerization Dynamics of CH2=CHCHO in Solution J. Chem. Phys. 2010, 132, 124510 1-10
12. Parsons, B. F.; Szpunar, D. E.; Buttler, L. J. H-Atom High-n Rydberg Time-of-Flight Spectroscopy of C-H Bond Fission in Acrolein Dissociated at 193 nm J. Chem. Phys. 2002, 117, 7889-7895
13. Lee, A. M. D.; Coe, J. D.; Ullrich, S.; Ho, M.-L.; Lee, S.-J.; Cheng, B.-M.; Zgierski, M. Z.; Chen, I.-C.; Martinez, T. J.; Stolow, A. Substituent Effects on Dynamics at Conical Intersections: α,β-Enones J. Phys. Chem. A 2007, 111, 11948-11960
14. Haas, B. M.; Minton, T. K.; Felder, P.; Huber, J. R. Photodissociation of Acrolein and Propynal at 193 nm in a Molecular Beam. Primary and Secondary Reactions J. Phys. Chem. 1991, 95, 5149-5159
15. Shu, J.; Peterka, D. S.; Leone, S. R.; Ahmed, M. J. Tunable Synchrotron Vacuum Ultraviolet Ionization, Time-of-Flight Investigation of the Photodissociation of trans-Crotonaldehyde at 193 nm Phys. Chem. A 2004, 108, 7895-7902
16. Kao, Y.-T.; Chen, W.-C.; Yu, C.-H.; Chen, I.-C. Production of HCO from Propenal Photolyzed at 193 nm: Relaxation of Excited States and Distribution of Internal States of Fragment HCO J. Chem. Phys. 2001, 114, 8964-8970
17. 1 Acrolein J. Chem. Phys. 2000, 113, 184-191
18. Reguero, M.; Bernardi, F.; Olivucci, M.; Robb, M. A. A Model Study of the Mechanism of the Type B (Di-π-methane) and Lumiketone Rearrangement in Rotationally Constrained α,β-Enones J. Org. Chem. 1997, 62, 6897-6902
19. Bonneau, R. Transient Species in Photochemistry of Enones. The Orthogonal Triplet State Revealed by Laser Photolysis J. Am. Chem. Soc. 1980, 102, 3816-3822
20. Caldwell, R. A.; Tang, W.; Heibel, G. E.; Schuster, D. I. Nanosecond Kinetic Absorption and Calorimetric studies of Cyclopentenone: The Triplet, self-quenching, and the Predimerization Biradicals Photochem. Photobiol. 1991, 53, 159
21. Schuster, D. I.; Dunn, D. A.; Heibel, G. E.; Brown, P. B.; Rao, J. M.; Woning, J.; Bonneau, R. Dynamic Properties of Triplet Excited States of Cyclic Conjugated Enones as Revealed by Transient Absorption Spectroscopy J. Am. Chem. Soc. 1991, 113, 6245-6255
22. Devaquet, A. Potential Energy Sheets for the nπ* and ππ* Triplet States of α,β-Unsaturated Ketones J. Am. Chem. Soc. 1972, 94, 5160-5167
23. Schalk, O.; Lang, P.; Wu, G.; Schuurman, M. S.; Riedle, E.; Stolow, A. Internal Conversion vs. Intersystem Crossing What Drives the Dynamics of Cyclic α,β-Enones? Ultrafast Phenomena XVIII; EPJ Web of Conferences 41, 02031 (2013).
24. Riedle, E.; Bradler, M.; Sailer, C.; Wenninger, M.; Pugliesi, I. Electronic Transient Spectroscopy from the Deep UV to the NIR: Unambiguous Disentanglement of Complex Processes Faraday Discuss. 2013, 163, 139-158
25. Wu, G.; Boguslavskiy, A. E.; Schalk, O.; Schuurman, M. S.; Stolow, A. Ultrafast Non-adaibatic Dynamics of Methyl Substituted Ethylenes J. Chem. Phys. 2011, 135, 164309
26. Schalk, O.; Boguslavskiy, A. E.; Stolow, A.; Schuurman, M. Through-Bond Interactions and the Localization of Excited-State Dynamics J. Am. Chem. Soc. 2011, 133, 16451-16458
27. Eland, J. H. D.; Vieuxmaire, O.; Kinugawa, T.; Lablanquie, P.; Hall, R. I.; Penent, F. Complete Two-Electron Spectra in Double Photoionization: The Rare Gases Ar, Kr, and Xe Phys. Rev. Lett. 2003, 90, 053003
28. Eland, J. H. D.; Feifel, R. Double Ionization of ICN and BrCN Studied by a New Photoelectron-Photoion Coincidence Technique Chem. Phys. 2006, 327, 85-90
29. Feifel, R.; Eland, J. H. D.; Storchi, L.; Tarantelli, F. An Experimental and Theoretical Study of Double Photoionization of CF4 Using Time-of-Flight Photoelectron-Photoelectron (Photoion-Photoion) Coincidence Spectroscopy J. Chem. Phys. 2006, 125, 194318
30. Lochbrunner, S.; Larsen, J.; Shaffer, J.; Schmitt, M.; Schultz, T.; Underwood, J.; Stolow, A. Methods and Applications of Femtosecond Time-Resolved Photoelectron Spectroscopy J. Electron Spectrosc. Relat. Phenom. 2000, 112, 183-198
31. Even, U.; Jortner, J.; Noy, D.; Lavie, N.; Cossart-Magos, C. Cooling of Large Molecules Below 1 K and He Clusters Formation J. Chem. Phys. 2000, 112, 8068-8071
32. Pierloot, K.; Dumez, B.; Widmar, P.-O.; Roos, B. O. Density-Matrix Averaged Atomic Natural Orbital (ANO) Basis-Sets for Correlated Molecular Wave-Functions. 4. Medium-Sized Basis-Sets for the Atoms H-Kr Theor. Chem. Acc. 1995, 90, 87-114
33. Stanton, J. F.; Gauss, J.; Harding, M. E.; Szalay, P. G. 32, Coupled-Cluster techniques for Computational Chemistry, a quantum-chemical program package. Current version: http://www.32.de.
34. Lischka, H.; Shepard, R.; Shavitt, I.; Pitzer, R. M.; Dallos, M.; Müller, Th.; Szalay, P. G.; Brown, F. B.; Ahlrichs, R.; Böhm, H. J.; COLUMBUS, an Ab Initio Electronic Structure Program, Release 7.0 (2012).
35. Langhoff, S. R.; Davidson, E. R. Configuration Interaction Calculations on the Nitrogen Molecule Int. J. Quantum Chem. 1974, 8, 61-72
36. Werner, H.-J.; Knowles, P. J.; Knizia, G.; Manby, F. R.; Schütz, M.; Celani, P.; Koronea, T.; Lidh, R.; Mitrushenkov, A.; Rauhut, G. MOLPRO, Version 2012.1, A Package of Ab Initio Programs, Cardiff, UK, 2012. Current Version: http://www.molpro.net.
37. Masclet, P.; Mouvier, G. étude par Spectrométrie Photoelectronique d'Aldéhydes et de Cétones éthé lyniques Conjugés J. Electron Spectrosc. Relat. Phenom. 1978, 14, 77-97
38. Kimura, K.; Katsumata, S.; Achiba, Y.; Yamazaki, Y.; Iwata, S. Handbook of HeI Photoelectron Spectra of Fundamental Organic Molecules; Japan Scientific Societies Press: Tokyo, 1981.
39. Levine, B. G.; Martinez, T. J. Isomerization Through Conical Intersections Annu. Rev. Phys. Chem. 2007, 58, 613-634
40. Stolow, A.; Underwood, J. G. Time-Resolved Photoelectron Spectroscopy of Nonadiabatic Dynamics in Polyatomic Molecules Adv. Chem. Phys. 2008, 139, 497-583
41. Schalk, O.; Boguslavskiy, A. E.; Stolow, A. Substituent Effects on Dynamics at Conical Intersections: Cyclopentadienes J. Phys. Chem. A 2010, 114, 4058-4064
42. Schalk, O.; Boguslavskiy, A. E.; Schuurman, M. S.; Broogard, R. Y.; Unterreiner, A. N.; Wrona-Piotrowicz, A.; Werstiuk, N. H.; Stolow, A. Substituent Effects on Dynamics at Conical Intersections: Cycloheptatrienes J. Phys Chem A 2013, 117, 10239-10247
43. 1 (nπ*) Electronic Excited State J. Chem. Phys. 1991, 94, 7734-7743
44. McGlynn, S. P.; Azumi, T.; Kinoshita, M. Molecular Spectroscopy of the Triplet State; Prentice Hall: New York, 1969.
45. Kuhlman, T. S.; Glover, W. J.; Mori, T.; Moller, K. B.; Martinez, T. J. Between Ethylene and Polyenes the Non-Adiabatic Dynamics of cis-Dienes Faraday Disuss. 2012, 157, 193-212
46. Nesbitt, D. J.; Field, R. W. Vibrational Energy Flow in Highly Excited Molecules: Role of Intramolecular Vibrational Redistribution J. Phys. Chem. 1996, 100, 12735-12756
47. Schalk, O.; Yang, J. P.; Hertwig, A.; Hippler, H.; Unterreiner, A.-N. Vibrational Cooling in the Liquid Phase Studied by Ultrafast Investigations of Cycloheptatriene Mol. Phys. 2009, 107, 2159-2167