The unimolecular loss of HF by simple inorganic ions: A computational Dynamic Reaction Path study

European Journal of Mass Spectrometry

Volumn 6, Issue 1, 2000, Pages 31-37

  Aschi, Massimiliano ^a   Grandinetti, Felice ^b  

^a SAPIENZA UNIVERSITY OF ROME   (Italy)

^b UNIVERSITY OF TUSCIA   (Italy)

Author keywords

DRC; Inorganic ions; Molecular dynamics; Unimolecular dissociations

Indexed keywords

EID: 0034395685     PISSN: 14690667     EISSN: None     Source Type: Journal    
DOI: 10.1255/ejms.327     Document Type: Article

References (40)

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34. Such result is not surprising since the tunnel effect has already been demonstrated to play a certain role in MIKE experiments. See for example: G. Hvistendhal and E. Uggerud, Org. Mass Spectrom. 26, 67 (1991).
35. Such assumption cannot be extended to the internal motions orthogonal to the reaction path, which are internally populated so to originate the zero-point energy of the TS. This contribution cannot be rigorously accounted for using classical dynamics and is usually taken into account by statistical arguments based on a number of calculated trajectories which is typically as large as thousands [see for example: (a) E.M. Goldfield, P.L. Houston and G.S. Ezra, J. Chem. Phys. 84,3120 (1986); (b) N.E. Henriksen, V. Engel and R. Schinke, J. Chem. Phys. 86, 6862 (1987); H. Tachikawa, Chem. Phys. 244, 263 (1999)]. However, as already made in previous related studies (see, for example, Reference 8a), we realised that, in the present case, such an exhaustive approach was not only prohibitively time-consuming but also unnecessary to get the qualitative information we were interested to.
36. Such assumption cannot be extended to the internal motions orthogonal to the reaction path, which are internally populated so to originate the zero-point energy of the TS. This contribution cannot be rigorously accounted for using classical dynamics and is usually taken into account by statistical arguments based on a number of calculated trajectories which is typically as large as thousands [see for example: (a) E.M. Goldfield, P.L. Houston and G.S. Ezra, J. Chem. Phys. 84,3120 (1986); (b) N.E. Henriksen, V. Engel and R. Schinke, J. Chem. Phys. 86, 6862 (1987); H. Tachikawa, Chem. Phys. 244, 263 (1999)]. However, as already made in previous related studies (see, for example, Reference 8a), we realised that, in the present case, such an exhaustive approach was not only prohibitively time-consuming but also unnecessary to get the qualitative information we were interested to.
37. Such assumption cannot be extended to the internal motions orthogonal to the reaction path, which are internally populated so to originate the zero-point energy of the TS. This contribution cannot be rigorously accounted for using classical dynamics and is usually taken into account by statistical arguments based on a number of calculated trajectories which is typically as large as thousands [see for example: (a) E.M. Goldfield, P.L. Houston and G.S. Ezra, J. Chem. Phys. 84,3120 (1986); (b) N.E. Henriksen, V. Engel and R. Schinke, J. Chem. Phys. 86, 6862 (1987); H. Tachikawa, Chem. Phys. 244, 263 (1999)]. However, as already made in previous related studies (see, for example, Reference 8a), we realised that, in the present case, such an exhaustive approach was not only prohibitively time-consuming but also unnecessary to get the qualitative information we were interested to.
38. All the trajectories are available as compressed files upon request.
39. Whenever possible "colder" INCs were generated and let to dissociate unimolecularly (see References 10-13). The resulted Ts appeared as totally different, generating narrow gaussian peaks indicative of a more statistical-like behaviour.
40. A. Yokoyama and T. Takayanagi, Chem. Phys. Lett. 307, 48 (1999).