Publication type: | Article in scientific journal |
Type of review: | Peer review (publication) |
Title: | Combined multidimensional anharmonic and parity violating effects in CDBrClF |
Authors: | Quack, Martin Stohner, Jürgen |
DOI: | 10.1063/1.1622381 |
Published in: | The Journal of Chemical Physics |
Volume(Issue): | 119 |
Issue: | 21 |
Page(s): | 11228 |
Pages to: | 11240 |
Issue Date: | 2003 |
Publisher / Ed. Institution: | American Institute of Physics |
ISSN: | 0021-9606 1089-7690 |
Language: | English |
Subject (DDC): | 540: Chemistry |
Abstract: | Parity violation causes rovibrational frequency shifts in infrared and microwave spectra between the corresponding lines of enantiomers of chiral molecules. In previous theoretical treatments of this effect simple harmonic and anharmonic adiabatic approximations were used which assumed that the vibrational potential as well as the parity violating potential are separable in normal (or local) coordinates. In the present work we investigate in detail the influence of nonseparable anharmonic couplings on vibrational frequency shifts caused by the parity violating potential in CDBrClF. We use the strongly coupled four-dimensional CD- and CF-chromophore subspaces and discuss how relative frequency shifts are influenced by coupling in the pure vibrational potential as well as in the parity violating potential. A four-dimensional parity violating potential energy hypersurface has been determined ab initio and fitted to a polynomial expansion. We analyze the nonseparable multidimensional representation of the parity violating potential in a chiral molecule. The effects of the multidimensional anharmonic couplings provide the dominant corrections. They are found to be about 20% for the expectation value of the parity violating energy difference ΔpvE between enantiomers (coupled ΔpvE/hc≈1.76×10−12 cm−1 compared to 1.96×10−12 cm−1 uncoupled). The corrections due to anharmonic multidimensional coupling can be more than a factor of 2 for vibrational frequency shifts, depending on the mode considered. |
URI: | https://digitalcollection.zhaw.ch/handle/11475/4517 |
Fulltext version: | Published version |
License (according to publishing contract): | Licence according to publishing contract |
Departement: | Life Sciences and Facility Management |
Appears in collections: | Publikationen Life Sciences und Facility Management |
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Quack, M., & Stohner, J. (2003). Combined multidimensional anharmonic and parity violating effects in CDBrClF. The Journal of Chemical Physics, 119(21), 11228–11240. https://doi.org/10.1063/1.1622381
Quack, M. and Stohner, J. (2003) ‘Combined multidimensional anharmonic and parity violating effects in CDBrClF’, The Journal of Chemical Physics, 119(21), pp. 11228–11240. Available at: https://doi.org/10.1063/1.1622381.
M. Quack and J. Stohner, “Combined multidimensional anharmonic and parity violating effects in CDBrClF,” The Journal of Chemical Physics, vol. 119, no. 21, pp. 11228–11240, 2003, doi: 10.1063/1.1622381.
QUACK, Martin und Jürgen STOHNER, 2003. Combined multidimensional anharmonic and parity violating effects in CDBrClF. The Journal of Chemical Physics. 2003. Bd. 119, Nr. 21, S. 11228–11240. DOI 10.1063/1.1622381
Quack, Martin, and Jürgen Stohner. 2003. “Combined Multidimensional Anharmonic and Parity Violating Effects in CDBrClF.” The Journal of Chemical Physics 119 (21): 11228–40. https://doi.org/10.1063/1.1622381.
Quack, Martin, and Jürgen Stohner. “Combined Multidimensional Anharmonic and Parity Violating Effects in CDBrClF.” The Journal of Chemical Physics, vol. 119, no. 21, 2003, pp. 11228–40, https://doi.org/10.1063/1.1622381.
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