Ab initio calculations of the geometry and vibrational frequencies of the triplet state of tungsten pentacarbonyl amine: A model for the unification of the preresonance Raman and the time-resolved infrared experiments
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1997
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Ab initio calculations of the vibrational frequencies of W(CO)(5)NH3 in its ground electronic (1)A(1) (b(2)(2)e(4)) and lowest excited state (3)E (b(2)(2)e(3)a(1)(1)) have been performed at the HF level. The calculated frequencies of the nu(CO) bands are in agreement with observed data on experimentally studied W(CO)(5)(amine) molecules. The optimized geometries of the ground and the excited states show that the W-N, W-C-eq, W-C-ax, C-O-eq bonds lengthen and the C-O-ax bond shortens on excitation. Our results resolve an apparent disagreement between the fast time-resolved infrared (TRIR) spectroscopy and the preresonance Raman (PRR) spectroscopy. The unexpected simultaneous lengthening of both W-C-eq and C-O-eq is due to C-O-eq antibonding character in the a(1) orbital which more than offsets its loss from the e. In addition a new band, predicted but as yet unresolved in the TRIR, accounts for the C-O-ax shortening as expected from the PRR W-C-ax lengthening.
Izvor:
Journal of the American Chemical Society, 1997, 119, 12, 2885-2888Izdavač:
- Amer Chemical Soc, Washington
DOI: 10.1021/ja9612662
ISSN: 0002-7863
WoS: A1997WQ02000016
Scopus: 2-s2.0-0030887951
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Institucija/grupa
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Zarić, Snežana D. AU - Couty, M AU - Hall, Michael B. PY - 1997 UR - https://cherry.chem.bg.ac.rs/handle/123456789/2588 AB - Ab initio calculations of the vibrational frequencies of W(CO)(5)NH3 in its ground electronic (1)A(1) (b(2)(2)e(4)) and lowest excited state (3)E (b(2)(2)e(3)a(1)(1)) have been performed at the HF level. The calculated frequencies of the nu(CO) bands are in agreement with observed data on experimentally studied W(CO)(5)(amine) molecules. The optimized geometries of the ground and the excited states show that the W-N, W-C-eq, W-C-ax, C-O-eq bonds lengthen and the C-O-ax bond shortens on excitation. Our results resolve an apparent disagreement between the fast time-resolved infrared (TRIR) spectroscopy and the preresonance Raman (PRR) spectroscopy. The unexpected simultaneous lengthening of both W-C-eq and C-O-eq is due to C-O-eq antibonding character in the a(1) orbital which more than offsets its loss from the e. In addition a new band, predicted but as yet unresolved in the TRIR, accounts for the C-O-ax shortening as expected from the PRR W-C-ax lengthening. PB - Amer Chemical Soc, Washington T2 - Journal of the American Chemical Society T1 - Ab initio calculations of the geometry and vibrational frequencies of the triplet state of tungsten pentacarbonyl amine: A model for the unification of the preresonance Raman and the time-resolved infrared experiments VL - 119 IS - 12 SP - 2885 EP - 2888 DO - 10.1021/ja9612662 ER -
@article{ author = "Zarić, Snežana D. and Couty, M and Hall, Michael B.", year = "1997", abstract = "Ab initio calculations of the vibrational frequencies of W(CO)(5)NH3 in its ground electronic (1)A(1) (b(2)(2)e(4)) and lowest excited state (3)E (b(2)(2)e(3)a(1)(1)) have been performed at the HF level. The calculated frequencies of the nu(CO) bands are in agreement with observed data on experimentally studied W(CO)(5)(amine) molecules. The optimized geometries of the ground and the excited states show that the W-N, W-C-eq, W-C-ax, C-O-eq bonds lengthen and the C-O-ax bond shortens on excitation. Our results resolve an apparent disagreement between the fast time-resolved infrared (TRIR) spectroscopy and the preresonance Raman (PRR) spectroscopy. The unexpected simultaneous lengthening of both W-C-eq and C-O-eq is due to C-O-eq antibonding character in the a(1) orbital which more than offsets its loss from the e. In addition a new band, predicted but as yet unresolved in the TRIR, accounts for the C-O-ax shortening as expected from the PRR W-C-ax lengthening.", publisher = "Amer Chemical Soc, Washington", journal = "Journal of the American Chemical Society", title = "Ab initio calculations of the geometry and vibrational frequencies of the triplet state of tungsten pentacarbonyl amine: A model for the unification of the preresonance Raman and the time-resolved infrared experiments", volume = "119", number = "12", pages = "2885-2888", doi = "10.1021/ja9612662" }
Zarić, S. D., Couty, M.,& Hall, M. B.. (1997). Ab initio calculations of the geometry and vibrational frequencies of the triplet state of tungsten pentacarbonyl amine: A model for the unification of the preresonance Raman and the time-resolved infrared experiments. in Journal of the American Chemical Society Amer Chemical Soc, Washington., 119(12), 2885-2888. https://doi.org/10.1021/ja9612662
Zarić SD, Couty M, Hall MB. Ab initio calculations of the geometry and vibrational frequencies of the triplet state of tungsten pentacarbonyl amine: A model for the unification of the preresonance Raman and the time-resolved infrared experiments. in Journal of the American Chemical Society. 1997;119(12):2885-2888. doi:10.1021/ja9612662 .
Zarić, Snežana D., Couty, M, Hall, Michael B., "Ab initio calculations of the geometry and vibrational frequencies of the triplet state of tungsten pentacarbonyl amine: A model for the unification of the preresonance Raman and the time-resolved infrared experiments" in Journal of the American Chemical Society, 119, no. 12 (1997):2885-2888, https://doi.org/10.1021/ja9612662 . .