Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution: Predicting Band Shapes in One- and Two-Photon Absorption Spectra of Chalcones
We have examined several approaches relying on the Polarizable Embedding (PE) scheme to predict optical band shapes for two chalcone molecules in methanol solution. The PE-TDDFT and PERI-CC2 methods were combined with molecular dynamics simulations, where the solute geometry was kept either as rigid...
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/22/10/1643 |
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doaj-ed6fe81bf014413d964d0f42cad31f9f2020-11-24T20:49:02ZengMDPI AGMolecules1420-30492017-09-012210164310.3390/molecules22101643molecules22101643Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution: Predicting Band Shapes in One- and Two-Photon Absorption Spectra of ChalconesJoanna Bednarska0Robert Zaleśny1Guangjun Tian2Natarajan Arul Murugan3Hans Ågren4Wojciech Bartkowiak5Department of Physical and Quantum Chemistry, Faculty of Chemistry, Wrocław University of Science and Technology, Wyb. Wyspiańskiego 27, PL-50370 Wrocław, PolandDepartment of Physical and Quantum Chemistry, Faculty of Chemistry, Wrocław University of Science and Technology, Wyb. Wyspiańskiego 27, PL-50370 Wrocław, PolandHebei Key Laboratory of Microstructural Material Physics, School of Science, Yanshan University, Qinhuangdao 066004, ChinaDivision of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, SE–10691 Stockholm, SwedenDivision of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, SE–10691 Stockholm, SwedenDepartment of Physical and Quantum Chemistry, Faculty of Chemistry, Wrocław University of Science and Technology, Wyb. Wyspiańskiego 27, PL-50370 Wrocław, PolandWe have examined several approaches relying on the Polarizable Embedding (PE) scheme to predict optical band shapes for two chalcone molecules in methanol solution. The PE-TDDFT and PERI-CC2 methods were combined with molecular dynamics simulations, where the solute geometry was kept either as rigid, flexible or partly-flexible (restrained) body. The first approach, termed RBMD-PE-TDDFT, was employed to estimate the inhomogeneous broadening for subsequent convolution with the vibrationally-resolved spectra of the molecule in solution determined quantum-mechanically (QM). As demonstrated, the RBMD-PE-TDDFT/QM-PCM approach delivers accurate band widths, also reproducing their correct asymmetric shapes. Further refinement can be obtained by the estimation of the inhomogeneous broadening using the RBMD-PERI-CC2 method. On the other hand, the remaining two approaches (FBMD-PE-TDDFT and ResBMD-PE-TDDFT), which lack quantum-mechanical treatment of molecular vibrations, lead to underestimated band widths. In this study, we also proposed a simple strategy regarding the rapid selection of the exchange-correlation functional for the simulations of vibrationally-resolved one- and two-photon absorption spectra based on two easy-to-compute metrics.https://www.mdpi.com/1420-3049/22/10/1643density functional theorytwo-photon absorptionvibrationally-resolved spectrahybrid QM/MM solvation models |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Joanna Bednarska Robert Zaleśny Guangjun Tian Natarajan Arul Murugan Hans Ågren Wojciech Bartkowiak |
| spellingShingle |
Joanna Bednarska Robert Zaleśny Guangjun Tian Natarajan Arul Murugan Hans Ågren Wojciech Bartkowiak Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution: Predicting Band Shapes in One- and Two-Photon Absorption Spectra of Chalcones Molecules density functional theory two-photon absorption vibrationally-resolved spectra hybrid QM/MM solvation models |
| author_facet |
Joanna Bednarska Robert Zaleśny Guangjun Tian Natarajan Arul Murugan Hans Ågren Wojciech Bartkowiak |
| author_sort |
Joanna Bednarska |
| title |
Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution: Predicting Band Shapes in One- and Two-Photon Absorption Spectra of Chalcones |
| title_short |
Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution: Predicting Band Shapes in One- and Two-Photon Absorption Spectra of Chalcones |
| title_full |
Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution: Predicting Band Shapes in One- and Two-Photon Absorption Spectra of Chalcones |
| title_fullStr |
Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution: Predicting Band Shapes in One- and Two-Photon Absorption Spectra of Chalcones |
| title_full_unstemmed |
Nonempirical Simulations of Inhomogeneous Broadening of Electronic Transitions in Solution: Predicting Band Shapes in One- and Two-Photon Absorption Spectra of Chalcones |
| title_sort |
nonempirical simulations of inhomogeneous broadening of electronic transitions in solution: predicting band shapes in one- and two-photon absorption spectra of chalcones |
| publisher |
MDPI AG |
| series |
Molecules |
| issn |
1420-3049 |
| publishDate |
2017-09-01 |
| description |
We have examined several approaches relying on the Polarizable Embedding (PE) scheme to predict optical band shapes for two chalcone molecules in methanol solution. The PE-TDDFT and PERI-CC2 methods were combined with molecular dynamics simulations, where the solute geometry was kept either as rigid, flexible or partly-flexible (restrained) body. The first approach, termed RBMD-PE-TDDFT, was employed to estimate the inhomogeneous broadening for subsequent convolution with the vibrationally-resolved spectra of the molecule in solution determined quantum-mechanically (QM). As demonstrated, the RBMD-PE-TDDFT/QM-PCM approach delivers accurate band widths, also reproducing their correct asymmetric shapes. Further refinement can be obtained by the estimation of the inhomogeneous broadening using the RBMD-PERI-CC2 method. On the other hand, the remaining two approaches (FBMD-PE-TDDFT and ResBMD-PE-TDDFT), which lack quantum-mechanical treatment of molecular vibrations, lead to underestimated band widths. In this study, we also proposed a simple strategy regarding the rapid selection of the exchange-correlation functional for the simulations of vibrationally-resolved one- and two-photon absorption spectra based on two easy-to-compute metrics. |
| topic |
density functional theory two-photon absorption vibrationally-resolved spectra hybrid QM/MM solvation models |
| url |
https://www.mdpi.com/1420-3049/22/10/1643 |
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