Molecular Vibrational Dynamics in Solution Investigated by Stationary and Time-Resolved Infrared Spectroscopy
Molecular Vibrational Dynamics in Solution Investigated by Stationary and Time-Resolved Infrared Spectroscopy
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DissertationDate of Exam
27.09.2021Date of Publication
19.11.2021Advisor
Vöhringer, PeterCo-Referee
Kirchner, BarbaraMetadata
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Abstract
Within this thesis, the time-resolved pump-probe and the two-dimensional mid-infrared spectroscopy were applied to investigate ultrafast processes in the condensed phase. Therefore, the stretching vibration υ3 of the cyanate anion or the carbon dioxide were selected as a vibrational probe for the studies of their aqueous solutions under isobaric heating from 303 K up to 603 K. Herein, the time constants of the vibrational energy relaxation and the underlying mechanism were unraveled. For cyanate and carbon dioxide in aqueous solution, a solvent-assisted sequential intramolecular vibrational redistribution was considered. Within this mechanism, the vibrational excess energy is intramolecular redistributed from the initially excited υ3 into the bending mode. From here, the energy is transferred to a solvent’s resonant mode, where the excess energy is subsequently redistributed within the solvent. The time constants of the intermolecular energy transfer to the solvent’s resonant mode were observed by the time-resolved pump-probe spectroscopy. In case of the CO2/H2O system, the time constant of the intramolecular energy redistribution was obtained from the correlation time used for the simulation of the temperature-dependent stationary infrared spectra based on the Kubo-Anderson general stochastic theory. The vibrational energy relaxation mechanisms of the investigated OCN– and CO2 aqueous solutions were then classified into and discussed in the context of the series of other pseudohalide anions, which were investigated earlier.
The two-dimensional mid-IR spectroscopy was applied to investigate the intramolecular dynamics of trans-4-methoxybut-3-en-2-one and its rotamers in C2Cl4. The υ(C=C) and the υ(C=O) stretching vibrations were used as vibrational probes. The two-dimensional infrared spectra were then analyzed in the context to assign the cross peaks to the corresponding vibrational modes of the different rotamers of this molecule.
Furthermore, the conformational dynamics were investigated. The occurrence of additional cross peaks at the earliest delay time of 600 fs were attributed to a dimerization of two rotamers in solution.
The two-dimensional mid-IR spectroscopy was applied to investigate the intramolecular dynamics of trans-4-methoxybut-3-en-2-one and its rotamers in C2Cl4. The υ(C=C) and the υ(C=O) stretching vibrations were used as vibrational probes. The two-dimensional infrared spectra were then analyzed in the context to assign the cross peaks to the corresponding vibrational modes of the different rotamers of this molecule.
Furthermore, the conformational dynamics were investigated. The occurrence of additional cross peaks at the earliest delay time of 600 fs were attributed to a dimerization of two rotamers in solution.
Subjects
Ultrakurzzeitspektroskopie, Schwingungsenergietransfer, kondensierte Phase, Kohlenstoffdioxid, Pseudohalogenide, Fermis Goldene Regel, time-resolved infrared spectroscopy, vibrational dynamics, carbon dioxide, pseudohalide anions, condensed matter
Classification (DDC)
540 ChemieGleim, Jeannine: Molecular Vibrational Dynamics in Solution Investigated by Stationary and Time-Resolved Infrared Spectroscopy. - Bonn, 2021. - Dissertation, Rheinische Friedrich-Wilhelms-Universität Bonn.
Online-Ausgabe in bonndoc: https://nbn-resolving.org/urn:nbn:de:hbz:5-64636
Online-Ausgabe in bonndoc: https://nbn-resolving.org/urn:nbn:de:hbz:5-64636
@phdthesis{handle:20.500.11811/9415,
urn: https://nbn-resolving.org/urn:nbn:de:hbz:5-64636,
author = {{Jeannine Gleim}},
title = {Molecular Vibrational Dynamics in Solution Investigated by Stationary and Time-Resolved Infrared Spectroscopy},
school = {Rheinische Friedrich-Wilhelms-Universität Bonn},
year = 2021,
month = nov,
note = {Within this thesis, the time-resolved pump-probe and the two-dimensional mid-infrared spectroscopy were applied to investigate ultrafast processes in the condensed phase. Therefore, the stretching vibration υ3 of the cyanate anion or the carbon dioxide were selected as a vibrational probe for the studies of their aqueous solutions under isobaric heating from 303 K up to 603 K. Herein, the time constants of the vibrational energy relaxation and the underlying mechanism were unraveled. For cyanate and carbon dioxide in aqueous solution, a solvent-assisted sequential intramolecular vibrational redistribution was considered. Within this mechanism, the vibrational excess energy is intramolecular redistributed from the initially excited υ3 into the bending mode. From here, the energy is transferred to a solvent’s resonant mode, where the excess energy is subsequently redistributed within the solvent. The time constants of the intermolecular energy transfer to the solvent’s resonant mode were observed by the time-resolved pump-probe spectroscopy. In case of the CO2/H2O system, the time constant of the intramolecular energy redistribution was obtained from the correlation time used for the simulation of the temperature-dependent stationary infrared spectra based on the Kubo-Anderson general stochastic theory. The vibrational energy relaxation mechanisms of the investigated OCN– and CO2 aqueous solutions were then classified into and discussed in the context of the series of other pseudohalide anions, which were investigated earlier.
The two-dimensional mid-IR spectroscopy was applied to investigate the intramolecular dynamics of trans-4-methoxybut-3-en-2-one and its rotamers in C2Cl4. The υ(C=C) and the υ(C=O) stretching vibrations were used as vibrational probes. The two-dimensional infrared spectra were then analyzed in the context to assign the cross peaks to the corresponding vibrational modes of the different rotamers of this molecule.
Furthermore, the conformational dynamics were investigated. The occurrence of additional cross peaks at the earliest delay time of 600 fs were attributed to a dimerization of two rotamers in solution.},
url = {https://hdl.handle.net/20.500.11811/9415}
}
urn: https://nbn-resolving.org/urn:nbn:de:hbz:5-64636,
author = {{Jeannine Gleim}},
title = {Molecular Vibrational Dynamics in Solution Investigated by Stationary and Time-Resolved Infrared Spectroscopy},
school = {Rheinische Friedrich-Wilhelms-Universität Bonn},
year = 2021,
month = nov,
note = {Within this thesis, the time-resolved pump-probe and the two-dimensional mid-infrared spectroscopy were applied to investigate ultrafast processes in the condensed phase. Therefore, the stretching vibration υ3 of the cyanate anion or the carbon dioxide were selected as a vibrational probe for the studies of their aqueous solutions under isobaric heating from 303 K up to 603 K. Herein, the time constants of the vibrational energy relaxation and the underlying mechanism were unraveled. For cyanate and carbon dioxide in aqueous solution, a solvent-assisted sequential intramolecular vibrational redistribution was considered. Within this mechanism, the vibrational excess energy is intramolecular redistributed from the initially excited υ3 into the bending mode. From here, the energy is transferred to a solvent’s resonant mode, where the excess energy is subsequently redistributed within the solvent. The time constants of the intermolecular energy transfer to the solvent’s resonant mode were observed by the time-resolved pump-probe spectroscopy. In case of the CO2/H2O system, the time constant of the intramolecular energy redistribution was obtained from the correlation time used for the simulation of the temperature-dependent stationary infrared spectra based on the Kubo-Anderson general stochastic theory. The vibrational energy relaxation mechanisms of the investigated OCN– and CO2 aqueous solutions were then classified into and discussed in the context of the series of other pseudohalide anions, which were investigated earlier.
The two-dimensional mid-IR spectroscopy was applied to investigate the intramolecular dynamics of trans-4-methoxybut-3-en-2-one and its rotamers in C2Cl4. The υ(C=C) and the υ(C=O) stretching vibrations were used as vibrational probes. The two-dimensional infrared spectra were then analyzed in the context to assign the cross peaks to the corresponding vibrational modes of the different rotamers of this molecule.
Furthermore, the conformational dynamics were investigated. The occurrence of additional cross peaks at the earliest delay time of 600 fs were attributed to a dimerization of two rotamers in solution.},
url = {https://hdl.handle.net/20.500.11811/9415}
}
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