Gas-Phase Formation of the Disilavinylidene (H2SiSi) Transient
Dr. Tao Yang
Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, 96822 USA
These authors contributed equally to this work.
Search for more papers by this authorDr. Beni B. Dangi
Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, 96822 USA
Department of Chemistry, Florida A&M University, Tallahassee, FL, 32307 USA
These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Prof. Dr. Ralf I. Kaiser
Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, 96822 USA
Search for more papers by this authorKang-Heng Chao
Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien, 974 Taiwan
Search for more papers by this authorDr. Bing-Jian Sun
Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien, 974 Taiwan
Search for more papers by this authorCorresponding Author
Prof. Dr. Agnes H. H. Chang
Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien, 974 Taiwan
Search for more papers by this authorDr. Thanh Lam Nguyen
Department of Chemistry, University of Texas at Austin, Austin, TX, 78712 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. John F. Stanton
Department of Chemistry, University of Texas at Austin, Austin, TX, 78712 USA
Search for more papers by this authorDr. Tao Yang
Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, 96822 USA
These authors contributed equally to this work.
Search for more papers by this authorDr. Beni B. Dangi
Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, 96822 USA
Department of Chemistry, Florida A&M University, Tallahassee, FL, 32307 USA
These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Prof. Dr. Ralf I. Kaiser
Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI, 96822 USA
Search for more papers by this authorKang-Heng Chao
Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien, 974 Taiwan
Search for more papers by this authorDr. Bing-Jian Sun
Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien, 974 Taiwan
Search for more papers by this authorCorresponding Author
Prof. Dr. Agnes H. H. Chang
Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien, 974 Taiwan
Search for more papers by this authorDr. Thanh Lam Nguyen
Department of Chemistry, University of Texas at Austin, Austin, TX, 78712 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. John F. Stanton
Department of Chemistry, University of Texas at Austin, Austin, TX, 78712 USA
Search for more papers by this authorAbstract
The hitherto elusive disilavinylidene (H2SiSi) molecule, which is in equilibrium with the mono-bridged (Si(H)SiH) and di-bridged (Si(H2)Si) isomers, was initially formed in the gas-phase reaction of ground-state atomic silicon (Si) with silane (SiH4) under single-collision conditions in crossed molecular beam experiments. Combined with state-of-the-art electronic structure and statistical calculations, the reaction was found to involve an initial formation of a van der Waals complex in the entrance channel, a submerged barrier to insertion, intersystem crossing (ISC) from the triplet to the singlet manifold, and hydrogen migrations. These studies provide a rare glimpse of silicon chemistry on the molecular level and shed light on the remarkable non-adiabatic reaction dynamics of silicon, which are quite distinct from those of isovalent carbon systems, providing important insight that reveals an exotic silicon chemistry to form disilavinylidene.
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References
- 1I. Langmuir, J. Am. Chem. Soc. 1919, 41, 1543–1559.
- 2M. McCarthy, P. Thaddeus, Phys. Rev. Lett. 2003, 90, 213003.
- 3H. Lee, J. H. Baraban, R. W. Field, J. F. Stanton, J. Phys. Chem. A 2013, 117, 11679–11683.
- 4M. M. Gallo, T. P. Hamilton, H. F. Schaefer III, J. Am. Chem. Soc. 1990, 112, 8714–8719.
- 5Y. Chen, D. M. Jonas, J. Kinsey, R. Field, J. Chem. Phys. 1989, 91, 3976–3987.
- 6S. A. B. Solina, J. P. O'Brie, R. W. Field, W. F. Polik, J. Phys. Chem. 1996, 100, 7797–7809.
- 7J. P. O'Brien, M. P. Jacobson, J. J. Sokol, S. L. Coy, R. W. Field, J. Chem. Phys. 1998, 108, 7100–7113.
- 8M. P. Jacobson, R. J. Silbey, R. W. Field, J. Chem. Phys. 1999, 110, 845–859.
- 9K. M. Ervin, J. Ho, W. C. Lineberger, J. Chem. Phys. 1989, 91, 5974–5992.
- 10J. Levin, H. Feldman, A. Baer, D. Ben-Hamu, O. Heber, D. Zajfman, Z. Vager, Phys. Rev. Lett. 1998, 81, 3347–3350.
- 11P. Ghana, M. I. Arz, U. Das, G. Schnakenburg, A. C. Filippou, Angew. Chem. Int. Ed. 2015, 54, 9980–9985; Angew. Chem. 2015, 127, 10118–10123.
- 12G. Maier, H. P. Reisenauer, J. Glatthaar, Chem. Eur. J. 2002, 8, 4383–4391.
10.1002/1521-3765(20021004)8:19<4383::AID-CHEM4383>3.0.CO;2-1 CAS PubMed Web of Science® Google Scholar
- 13M. Bogey, H. Bolvin, C. Demuynck, J. Destombes, Phys. Rev. Lett. 1991, 66, 413–416.
- 14M. Bogey, H. Bolvin, M. Cordonnier, C. Demuynck, J. Destombes, A. Császár, J. Chem. Phys. 1994, 100, 8614–8624.
- 15L. Andrews, X. Wang, J. Phys. Chem. A 2002, 106, 7696–7702.
- 16M. Cordonnier, M. Bogey, C. Demuynck, J. L. Destombes, J. Chem. Phys. 1992, 97, 7984–7989.
- 17S. Koseki, M. S. Gordon, J. Phys. Chem. 1989, 93, 118–125.
- 18B. T. Colegrove, H. F. Schaefer III, J. Phys. Chem. 1990, 94, 5593–5602.
- 19P. S. Weiss, PhD Thesis, University of California at Berkeley (USA), 1986.
- 20W. B. Miller, S. A. Safron, D. R. Herschbach, Discuss. Faraday Soc. 1967, 44, 108–122.
10.1039/df9674400108 Google Scholar
- 21R. S. Grev, H. F. Schaefer III, J. Chem. Phys. 1992, 97, 7990–7998.
- 22D. S. Parker, F. Zhang, Y. S. Kim, R. I. Kaiser, A. Landera, V. V. Kislov, A. M. Mebel, A. Tielens, Proc. Natl. Acad. Sci. USA 2012, 109, 53–58.
- 23T. Tanaka, M. Hiramatsu, M. Nawata, A. Kono, T. Goto, J. Phys. D 1994, 27, 1660–1663.
- 24M. Koi, K. Tonokura, A. Tezaki, M. Koshi, J. Phys. Chem. A 2003, 107, 4838–4842.
- 25A. H. H. Chang, A. Mebel, X.-M. Yang, S. Lin, Y. Lee, J. Chem. Phys. 1998, 109, 2748–2761.
- 26A. M. Mebel, W. M. Jackson, A. H. H. Chang, S. H. Lin, J. Am. Chem. Soc. 1998, 120, 5751–5763.
- 27X. Gu, R. I. Kaiser, A. M. Mebel, ChemPhysChem 2008, 9, 350–369.
- 28W. Sun, K. Yokoyama, J. C. Robinson, A. G. Suits, D. M. Neumark, J. Chem. Phys. 1999, 110, 4363–4368.
- 29W. H. Miller, Faraday Discuss. Chem. Soc. 1977, 62, 40–46.
- 30T. L. Nguyen, J. F. Stanton, J. R. Barker, Chem. Phys. Lett. 2010, 499, 9–15.
- 31G.-S. Kim, T. L. Nguyen, A. M. Mebel, S. H. Lin, M. T. Nguyen, J. Phys. Chem. A 2003, 107, 1788–1796.
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