Orientation dependence of the Na + CH3NO2 charge-transfer reaction
| Autor: | James N. Bull, Robert G. A. R. Maclagan, Peter W. Harland |
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| Rok vydání: | 2009 |
| Předmět: |
Steric effects
Chemical substance Nitromethane media_common.quotation_subject Biophysics Condensed Matter Physics Asymmetry Metal chemistry.chemical_compound chemistry Fragmentation (mass spectrometry) Chemical physics visual_art visual_art.visual_art_medium Physical and Theoretical Chemistry Atomic physics Ground state Molecular Biology Molecular beam media_common |
| Zdroj: | Molecular Physics. 107:1123-1137 |
| ISSN: | 1362-3028 0026-8976 |
| DOI: | 10.1080/00268970902755017 |
| Popis: | The reaction of atomic sodium with nitromethane, CH3NO2, was studied using the B3LYP//6-311++G(3df,3pd) level of theory to investigate the orientation dependence of the charge-transfer type reaction. Excellent agreement was found between ground state interaction potentials and recent molecular beam orientation experimental data for free and . CH3NO2 shows slight steric asymmetry for the approach geometry of Na, with reaction favouring attack from the NO2-end at relatively low (few eV) energies. Increasing reaction energy allows CH3-end orientations to become accessible and new fragmentation processes to occur. Results indicate that an interpretation involving charge-transfer at relatively large separation, where the positive metal core plays little role in the dynamics following charge-transfer would not be correct. Coulombic interactions through ion-pair formation facilitate these reactions and, in part, explain some of the previously reported experimental steric asymmetry on this system. Dipole-bound st... |
| Databáze: | OpenAIRE |
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