A QM/MM and QM/QM/MM study of Kerr, Cotton–Mouton and Jones linear birefringences in liquid acetonitrile
| Autor: | Jógvan Magnus Haugaard Olsen, Tobias Fahleson, Antonio Rizzo, Patrick Norman |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Linear birefringence
Cotton--Mouton Ab initio General Physics and Astronomy PDE 010402 general chemistry QM/MM 01 natural sciences Molecular physics Molecular dynamics chemistry.chemical_compound Teoretisk kemi 0103 physical sciences Theoretical chemistry Jones Acetonitrile Physical and Theoretical Chemistry Theoretical Chemistry Linear Birefringences Physics Detection limit Polarizable Density Embedding 010304 chemical physics Series (mathematics) Jones Birefringence Observable 0104 chemical sciences chemistry QM/QM/MM Kerr PE |
| Zdroj: | PCCP. Physical chemistry chemical physics 20 (2018): 3831–3840. doi:10.1039/C7CP07421B info:cnr-pdr/source/autori:T. Fahleson, J. M. H. Olsen, P. Norman and A. Rizzo/titolo:A QM%2FMM and QM%2FQM%2FMM study of Kerr, Cotton-Mouton and Jones linear birefringences in liquid acetonitrile/doi:10.1039%2FC7CP07421B/rivista:PCCP. Physical chemistry chemical physics (Print)/anno:2018/pagina_da:3831/pagina_a:3840/intervallo_pagine:3831–3840/volume:20 Fahleson, T, Olsen, J M H, Norman, P & Rizzo, A 2018, ' A QM/MM and QM/QM/MM study of Kerr, Cotton-Mouton and Jones linear birefringences in liquid acetonitrile ', Physical chemistry chemical physics : PCCP, vol. 20, no. 5, pp. 3831-3840 . https://doi.org/10.1039/c7cp07421b |
| ISSN: | 1463-9084 1463-9076 |
| DOI: | 10.1039/c7cp07421b |
| Popis: | QM/MM and QM/QM/MM protocols are applied to the ab initio study of the three linear birefringences Kerr, Cotton-Mouton, and Jones, as shown by acetonitrile in the gas and pure liquid phases. The relevant first-order properties as well as linear, quadratic, and cubic frequency-dependent response functions were computed using time-dependent Kohn-Sham density-functional theory with use of the standard CAM-B3LYP functional. In the liquid phase, a series of room temperature (293.15 K) molecular dynamics snapshots were selected, for which averaged values of the observables were obtained at an optical wavelength of 632.8 nm. The birefringences were computed for electric and magnetic induction fields corresponding to the laboratory setup previously employed by T. Roth and G. L. J. A. Rikken in Phys. Rev. Lett., 2000, 85, 4478. Under these conditions, acetonitrile is shown to exhibit a weak Jones response-in fact roughly 6.5 times smaller than the limit of detection of the apparatus employed in the measurements mentioned above. A comparison is made with the corresponding gas-phase results and an assessment is made of the index of measurability, estimating the degree of overlap of the three birefringences in actual measurements. For acetonitrile, it is shown that this index is a factor of 3.6 and 6.7 larger than that of methylcyclopentadienyl-Mn-tricarbonyl and cyclohexadienyl-Fe-tricarbonyl, respectively-two compounds reported in Phys. Rev. Lett., 2000, 85, 4478 to exhibit a strong Jones signal. |
| Databáze: | OpenAIRE |
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