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Vibrational assignment and Franck-Condon analysis of the mass-analyzed threshold ionization (MATI) spectrum of CH2ClI: the effect of strong spin-orbit interaction.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Lee, Mina Kim, Hyo-Seok Lee, Yong Siang Kim, Myung Soo |
| Copyright Year | 2005 |
| Abstract | Detailed analysis of the one-photon mass-analyzed threshold ionization (MATI) spectrum of CH(2)ClI is presented. This includes the determination of the ionization energy of CH(2)ClI, complete vibrational assignments, and quantum-chemical calculations at the spin-orbit density-functional-theory (SODFT) level with various basis sets. Relativistic effective core potentials with effective spin-orbit operators can be used in SODFT calculations to treat the spin-orbit term on an equal footing with other relativistic effects and electron correlations. The comparison of calculated and experimental vibrational frequencies indicate that the spin-orbit effects are essential for the reasonable description of the CH(2)ClI(+) cation. Geometrical parameters and thus the molecular shape of the cation are greatly influenced by the spin-orbit effects even for the ground state. Calculated geometrical parameters deviate substantially for different basis sets or effective core potentials. In an effort to derive the exact geometrical parameters for this cation, SODFT geometries were further improved utilizing Franck-Condon fit of the MATI spectral pattern. This empirical fitting produced the well-converged set of geometrical parameters that are quite insensitive to the choice of SODFT calculations. The C-I bond length and the Cl-C-I bond angle show large deviations among different SODFT calculations, but the empirical spectral fitting yields 2.191 +/- 0.003 Angstroms for the C-I bond length and 107.09 +/- 0.09 degrees for the Cl-C-I angle. Those fitted geometrical parameters along with the experimental vibrational frequencies could serve as a useful reference in calibrating relativistic quantum-chemical methods for radicals. |
| Starting Page | 244319 |
| Ending Page | 244319 |
| Page Count | 1 |
| File Format | PDF HTM / HTML |
| DOI | 10.1063/1.1948384 |
| PubMed reference number | 16035769 |
| Journal | Medline |
| Volume Number | 122 |
| Issue Number | 24 |
| Alternate Webpage(s) | http://mass.snu.ac.kr/journal/161.pdf |
| Alternate Webpage(s) | https://doi.org/10.1063/1.1948384 |
| Journal | The Journal of chemical physics |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
