Structural dynamics effects on the electronic predissociation of alkyl iodides.
Journal
Scientific reports
ISSN: 2045-2322
Titre abrégé: Sci Rep
Pays: England
ID NLM: 101563288
Informations de publication
Date de publication:
21 Apr 2020
21 Apr 2020
Historique:
received:
10
01
2020
accepted:
23
03
2020
entrez:
23
4
2020
pubmed:
23
4
2020
medline:
23
4
2020
Statut:
epublish
Résumé
The correlation between chemical structure and predissociation dynamics has been evaluated for a series of linear and branched alkyl iodides with increasing structural complexity by means of femtosecond time-resolved velocity map imaging experiments following excitation on the second absorption band (B-band) at around 201 nm. The time-resolved images for the iodine fragment are reported and analyzed in order to extract electronic predissociation lifetimes and the temporal evolution of the anisotropy while the experimental results are supported by ab initio calculations of the potential energy curves as a function of the C-I distance. Remarkable similarities are observed for all molecules consistent with a major predissociation of the initially populated bound Rydberg states 6A″ and 7A' through a crossing with the purely repulsive states 7A″, 8A' and 8A″ leading to a major R + I*(
Identifiants
pubmed: 32317645
doi: 10.1038/s41598-020-62982-0
pii: 10.1038/s41598-020-62982-0
pmc: PMC7174404
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
6700Références
Rosker, M. J., Dantus, M. & Zewail, A. H. Femtosecond clocking of the chemical bond. Science 241, 1200–1202 (1988).
doi: 10.1126/science.241.4870.1200
Corrales, M. E. et al. Structural dynamics effects on the ultrafast chemical bond cleavage of a photodissociation reaction. Phys. Chem. Chem. Phys. 16, 8812–8818 (2014).
doi: 10.1039/c3cp54677b
Gedanken, A. & Rowe, M. D. Magnetic circular dichroism spectra of the methyl halides. Resolution of the n→σ* continuum. Chem. Phys. Lett. 34, 39–43 (1975).
doi: 10.1016/0009-2614(75)80196-5
Murillo-Sánchez, M. L. et al. Halogen-atom effect on the ultrafast photodissociation dynamics of the dihalomethanes CH
doi: 10.1039/C8CP03600D
Gitzinger, G. et al. A femtosecond velocity map imaging study on B-band predissociation in CH
Thiré, N., Cireasa, R., Blanchet, V. & Pratt, S. T. Time-resolved photoelectron spectroscopy of the CH
doi: 10.1039/c004220j
Thiré, N. et al. Time-resolved predissociation of the vibrationless level of the B state of CH
Alekseyev, A. B., Liebermann, H.-P. & Buenker, R. J. Ab initio configuration interaction study of the B-and C-band photodissociation of methyl iodide. J. Chem. Phys. 134, 044303 (2011).
doi: 10.1063/1.3532926
Gitzinger, G., Corrales, M. E., Loriot, V., de Nalda, R. & Bañares, L. A femtosecond velocity map imaging study on B-band predissociation in CH
Eden, S., Limao-Vieira, P., Hoffmann, S. & Mason, N. VUV spectroscopy of CH
González, M. G., Rodríguez, J. D., Rubio-Lago, L. & Bañares, L. Communication: First observation of ground state I(
Xu, H. & Pratt, S. T. A new look at the photodissociation of methyl iodide at 193 nm. J. Chem. Phys. 139, 214310 (2013).
doi: 10.1063/1.4829747
Corrales, M. et al. Femtosecond time-resolved photofragment rotational angular momentum alignment in electronic predissociation dynamics. J. Phys. Chem. Lett. 7, 4458–4463 (2016).
doi: 10.1021/acs.jpclett.6b01874
Marggi Poullain, S. et al. Dynamics of the photodissociation of ethyl iodide from the origin of the B band. A slice imaging study. Phys. Chem. Chem. Phys. 21, 14250–14260 (2019).
doi: 10.1039/C8CP06482B
Murillo-Sánchez, M. L., Marggi Poullain, S., Loriot, V., Corrales, M. E. & Bañares, L. Femtosecond predissociation dynamics of ethyl iodide in the B-band. Phys. Chem. Chem. Phys. 21, 15695–15704 (2019).
doi: 10.1039/C9CP02992C
Boschi, R. & Salahub, D. The far ultra-violet spectra of some 1-iodoalkanes. Mol. Phys. 24, 289–299 (1972).
doi: 10.1080/00268977200101451
Boschi, R. & Salahub, D. The far ultra-violet spectra of some branched chain iodo-alkanes, iodo-cyclo-alkanes, fluoroiodo-alkanes and iodo-alkenes. Mol. Phys. 24, 735–752 (1972).
doi: 10.1080/00268977200101871
Limao-Vieira, P. Private communication.
Eppink, A. T. & Parker, D. Energy partitioning following photodissociation of methyl iodide in the A band: A velocity mapping study. J. Chem. Phys. 110, 832–844 (1999).
doi: 10.1063/1.478051
Eppink, A. T. & Parker, D. H. Methyl iodide A-band decomposition study by photofragment velocity imaging. J. Chem. Phys. 109, 4758–4767 (1998).
doi: 10.1063/1.477087
de Nalda, R. et al. A detailed experimental and theoretical study of the femtosecond A-band photodissociation of CH
doi: 10.1063/1.2943198
Eppink, A. T. & Parker, D. H. Velocity map imaging of ions and electrons using electrostatic lenses: Application in photoelectron and photofragment ion imaging of molecular oxygen. Rev. Sci. Instrum. 68, 3477–3484 (1997).
doi: 10.1063/1.1148310
García, G. A., Nahon, L. & Powis, I. Two-dimensional charged particle image inversion using a polar basis function expansion. Rev. Sci. Instrum. 75, 4989–4996 (2004).
doi: 10.1063/1.1807578
Loriot, V., Bañares, L. & de Nalda, R. Multidimensional analysis of time-resolved charged particle imaging experiments. Appl. Sci. 8, 1227 (2018).
doi: 10.3390/app8081227
Werner, H.-J. et al. MOLPRO, version 2009.1, a package of ab initio programs (2009).
Roos, B. O., Lindh, R., Malmqvist, P.-Å., Veryazov, V. & Widmark, P.-O. Main group atoms and dimers studied with a new relativistic ano basis set. The J. Phys. Chem. A 108, 2851–2858 (2004).
doi: 10.1021/jp031064+
Marante, C., Argenti, L. & Martín, F. Hybrid gaussian–b-spline basis for the electronic continuum: Photoionization of atomic hydrogen. Phys. Rev. A 90, 012506 (2014).
doi: 10.1103/PhysRevA.90.012506
Reiher, M. & Wolf, A. Exact decoupling of the Dirac hamiltonian. I. General theory. J. Chem. Phys. 121, 2037–2047 (2004).
Reiher, M. & Wolf, A. Exact decoupling of the Dirac hamiltonian. II. The generalized Douglas–Kroll–Hess transformation up to arbitrary order. The. J. Chem. Phys. 121, 10945–10956 (2004).
Peng, D. & Reiher, M. Exact decoupling of the relativistic Fock operator. Theor. Chem. Acc. 131, 1081 (2012).
Schimmelpfennig, B. AMFI, an atomic mean-field integral program. Stockholm University (1996).
Werner, H.-J. Third-order multireference perturbation theory. the CASPT3 method. Mol. Phys. 89, 645–661 (1996).
doi: 10.1080/002689796173967
Celani, P. & Werner, H.-J. Analytical energy gradients for internally contracted second-order multireference perturbation theory. J. Chem. Phys. 119, 5044–5057 (2003).
doi: 10.1063/1.1597672
Knowles, P. J. & Werner, H.-J. Internally contracted multiconfiguration-reference configuration interaction calculations for excited states. Theor. Chim. Acta 84, 95–103 (1992).
doi: 10.1007/BF01117405
Berning, A., Schweizer, M., Werner, H.-J., Knowles, P. J. & Palmieri, P. Spin-orbit matrix elements for internally contracted multireference configuration interaction wavefunctions. Mol. Phys. 98, 1823–1833 (2000).
doi: 10.1080/00268970009483386
Jung, Y.-J., Kim, Y. S., Kang, W. K. & Jung, K.-H. Photoelectron imaging spectroscopy for (2+1) resonance-enhanced multiphoton ionization of atomic iodine produced from a-band photolysis of CH
doi: 10.1063/1.474958
Moore, C. E. Atomic energy levels, vol. I. NBS circular 467, 949 (1949).
Zare, R. N. Angular Momentum: Understanding Spatial Aspects in Chemistry and Physics (Wiley, 1998).
Jonah, C. Effect of rotation and thermal velocity on the anisotropy in photodissociation spectroscopy. J. Chem. Phys. 55, 1915–1922 (1971).
doi: 10.1063/1.1676329
Yang, S. & Bersohn, R. Theory of the angular distribution of molecular photofragments. J. Chem. Phys. 61, 4400–4407 (1974).
doi: 10.1063/1.1681757
Pickett, H. M. The fitting and prediction of vibration-rotation spectra with spin interactions. J. Mol. Spectrosc. 148, 371–377 (1991).
doi: 10.1016/0022-2852(91)90393-O
Pickett, H. M. Spfit/spcat package.
Paterson, C., Godwin, F. & Gorry, P. Photofragmentation dynamics of C
Godwin, F., Paterson, C. & Gorry, P. Photofragmentation dynamics of n-C
Kim, Y. S., Kang, W. K., Kim, D.-C. & Jung, K.-H. Photodissociation of tert-butyl iodide at 277 and 304 nm: Evidence for direct and indirect dissociation in A-band photolysis of alkyl iodide. J. Phys. Chem. A 101, 7576–7581 (1997).
doi: 10.1021/jp970574z