Abstract
Nuclear Quadrupole Resonance (NQR) Nutation Spectroscopy studies and INDO calculations of the electronic structure of TiCl4 and its complexes have been performed. An explanation of the changes of the NQR frequencies and asymmetry parameters upon complex formation have been proposed. The populations of the TiCl4 orbitals have been estimated for different crystallographic structures and compared with the population of the TiCl42CH3CN orbitals. The values of the experimental 35Cl NQR frequencies correlated with the calculated ones. Moreover, there is good agreement between the experimentally determined and calculated nutation spectra asymmetry parameter for TiCl4. The results of the INDO calculations showed that the Ti-Cl bond order decreases upon complex formation and consequently the 35Cl NQR frequencies decrease and the asymmetry parameter increases. On the basis of the results of the quantum chemical calculations the population of the 3pπ chlorine orbital decreases when the molecular structure changes from TiCl4 (Td) to TiCl4 (D(4h)). The electron density transfer from the pπ orbital of the chlorine atom to the dπ orbital of the Ti atom decreases due to complex formation. It was found that the INDO method is suitable for determining the electron distribution in TiCl4 and its complexes.
| Original language | English |
|---|---|
| Pages (from-to) | 153-156 |
| Number of pages | 4 |
| Journal | Journal of Molecular Structure |
| Volume | 415 |
| Issue number | 1-2 |
| DOIs | |
| Publication status | Published - 11 Aug 1997 |
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Keywords
- Ab initio calculations
- INDO
- Nuclear quadrupole resonance spectroscopy
- Nutation spectroscopy
- Quantum chemical calculations
ASJC Scopus subject areas
- Structural Biology
- Organic Chemistry
- Physical and Theoretical Chemistry
- Spectroscopy
- Atomic and Molecular Physics, and Optics
Cite this
The asymmetry parameter of the electric field gradient tensor of TiCl4 and its complexes studied by NQR nutation spectroscopy. / Poleshchuk, O. Kh; Nogaj, B.; Latosińska, J. N.; Glaser, A.; Ostafin, M.
In: Journal of Molecular Structure, Vol. 415, No. 1-2, 11.08.1997, p. 153-156.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - The asymmetry parameter of the electric field gradient tensor of TiCl4 and its complexes studied by NQR nutation spectroscopy
AU - Poleshchuk, O. Kh
AU - Nogaj, B.
AU - Latosińska, J. N.
AU - Glaser, A.
AU - Ostafin, M.
PY - 1997/8/11
Y1 - 1997/8/11
N2 - Nuclear Quadrupole Resonance (NQR) Nutation Spectroscopy studies and INDO calculations of the electronic structure of TiCl4 and its complexes have been performed. An explanation of the changes of the NQR frequencies and asymmetry parameters upon complex formation have been proposed. The populations of the TiCl4 orbitals have been estimated for different crystallographic structures and compared with the population of the TiCl42CH3CN orbitals. The values of the experimental 35Cl NQR frequencies correlated with the calculated ones. Moreover, there is good agreement between the experimentally determined and calculated nutation spectra asymmetry parameter for TiCl4. The results of the INDO calculations showed that the Ti-Cl bond order decreases upon complex formation and consequently the 35Cl NQR frequencies decrease and the asymmetry parameter increases. On the basis of the results of the quantum chemical calculations the population of the 3pπ chlorine orbital decreases when the molecular structure changes from TiCl4 (Td) to TiCl4 (D(4h)). The electron density transfer from the pπ orbital of the chlorine atom to the dπ orbital of the Ti atom decreases due to complex formation. It was found that the INDO method is suitable for determining the electron distribution in TiCl4 and its complexes.
AB - Nuclear Quadrupole Resonance (NQR) Nutation Spectroscopy studies and INDO calculations of the electronic structure of TiCl4 and its complexes have been performed. An explanation of the changes of the NQR frequencies and asymmetry parameters upon complex formation have been proposed. The populations of the TiCl4 orbitals have been estimated for different crystallographic structures and compared with the population of the TiCl42CH3CN orbitals. The values of the experimental 35Cl NQR frequencies correlated with the calculated ones. Moreover, there is good agreement between the experimentally determined and calculated nutation spectra asymmetry parameter for TiCl4. The results of the INDO calculations showed that the Ti-Cl bond order decreases upon complex formation and consequently the 35Cl NQR frequencies decrease and the asymmetry parameter increases. On the basis of the results of the quantum chemical calculations the population of the 3pπ chlorine orbital decreases when the molecular structure changes from TiCl4 (Td) to TiCl4 (D(4h)). The electron density transfer from the pπ orbital of the chlorine atom to the dπ orbital of the Ti atom decreases due to complex formation. It was found that the INDO method is suitable for determining the electron distribution in TiCl4 and its complexes.
KW - Ab initio calculations
KW - INDO
KW - Nuclear quadrupole resonance spectroscopy
KW - Nutation spectroscopy
KW - Quantum chemical calculations
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UR - http://www.scopus.com/inward/citedby.url?scp=0030812395&partnerID=8YFLogxK
U2 - 10.1016/S0022-2860(97)00094-X
DO - 10.1016/S0022-2860(97)00094-X
M3 - Article
VL - 415
SP - 153
EP - 156
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
SN - 0022-2860
IS - 1-2
ER -