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Two-dimensional infrared (2D IR) spectroscopy, infrared pump–infrared probe spectroscopy, and density functional theory calculations were used to study vibrational relaxation by ring and carbonyl stretching modes in a series of methylated xanthine derivatives in acetonitrile and deuterium oxide (heavy water). Isotropic signals from the excited symmetric and asymmetric carbonyl stretch modes decay biexponentially in both solvents. Coherent energy transfer between the symmetric and asymmetric carbonyl stretching modes gives rise to a quantum beat in the time-dependent anisotropy signals. The damping time of the coherent oscillation agrees with the fast decay component of the carbonyl bleach recovery signals, indicating that this time constant reflects intramolecular vibrational redistribution (IVR) to other solute modes. Despite their similar frequencies, the excited ring modes decay monoexponentially with a time constant that matches the slow decay component of the carbonyl modes. The slow decay times, which are faster in heavy water than in acetonitrile, approximately match the ones observed in previous UV pump–IR probe measurements on the same compounds. The slow component is assigned to intermolecular energy transfer to solvent bath modes from low-frequency solute modes, which are populated by IVR and are anharmonically coupled to the carbonyl and ring stretch modes. 2D IR measurements indicate that the carbonyl stretching modes are weakly coupled to the delocalized ring modes, resulting in slow exchange that cannot explain the common solvent-dependence. IVR is suggested to occur at different rates for the carbonyl vs ring modes due to differences in mode-specific couplings and not to differences in the density of accessible states.
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Coherent ring-current migration of Mg-phthalocyanine probed by time-resolved X-ray circular dichroism
The coherent ring current of Mg-phthalocyanine are created by a broad band UV-visible pump pulse and migrate into different regions within the molecule. This coherent ring current dynamics is probed by time-resolved X-ray circular dichroism.
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- Award ID(s):
- 2246379
- PAR ID:
- 10501686
- Publisher / Repository:
- Chemical Science
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 13
- Issue:
- 35
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 10327 to 10335
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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