Vibrational relaxation in the condensed phase

Bakker, Huib J.

doi:10.1063/1.1808116

Cited by 30 publications

(21 citation statements)

References 22 publications

(24 reference statements)

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“…The latter correlation is consistent with previous reports 59,60 that vibrational relaxation is faster in more polar solvents, which has been attributed to stronger modulation of the vibrational energy levels. 59,61,62 Furthermore, vibrational relaxation in protic TFE is faster than in aprotic DMSO, although the latter has a higher dielectric constant. This suggests an additional speed-up of vibrational relaxation by hydrogen bonding.…”

Section: Polarity Of the Surroundings And Hydrogen Bonding Determine ...mentioning

confidence: 99%

Vibrational dynamics and solvatochromism of the label SCN in various solvents and hemoglobin by time dependent IR and 2D-IR spectroscopy

Wilderen

Kern-Michler

Müller‐Werkmeister

et al. 2014

Phys. Chem. Chem. Phys.

110

128

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We investigated the characteristics of the thiocyanate (SCN) functional group as a probe of local structural dynamics for 2D-IR spectroscopy of proteins, exploiting the dependence of vibrational frequency on the environment of the label. Steady-state and time-resolved infrared spectroscopy are performed on the model compound methylthiocyanate (MeSCN) in solvents of different polarity, and compared to data obtained on SCN as a local probe introduced as cyanylated cysteine in the protein bovine hemoglobin. The vibrational lifetime of the protein label is determined to be 37 ps, and its anharmonicity is observed to be lower than that of the model compound (which itself exhibits solvent-independent anharmonicity). The vibrational lifetime of MeSCN generally correlates with the solvent polarity, i.e. longer lifetimes in less polar solvents, with the longest lifetime being 158 ps. However, the capacity of the solvent to form hydrogen bonds complicates this simplified picture. The long lifetime of the SCN vibration is in contrast to commonly used azide labels or isotopically-labeled amide I and better suited to monitor structural rearrangements by 2D-IR spectroscopy. We present time-dependent 2D-IR data on the labeled protein which reveal an initially inhomogeneous structure around the CN oscillator. The distribution becomes homogeneous after 5 picoseconds so that spectral diffusion has effectively erased the 'memory' of the CN stretching frequency. Therefore, the 2D-IR data of the label incorporated in hemoglobin demonstrate how SCN can be utilized to sense rearrangements in the local structure on a picosecond timescale.

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Section: Polarity Of the Surroundings And Hydrogen Bonding Determine ...mentioning

confidence: 99%

Vibrational dynamics and solvatochromism of the label SCN in various solvents and hemoglobin by time dependent IR and 2D-IR spectroscopy

Wilderen

Kern-Michler

Müller‐Werkmeister

et al. 2014

Phys. Chem. Chem. Phys.

110

128

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“…Spectral broadening can assist in overcoming the energy mismatch between initial and final states. 25,26 To account for the spectral overlap of the absorption bands we assume a Lorentzian line shape for the OH band, whereas the overtone and combination tone bandwidths are assumed to be small compared to the OH band and thus, are taken as delta functions. Hence, the ␦ function in Eq.…”

Section: B Theorymentioning

confidence: 99%

Mode-selective O–H stretching relaxation in a hydrogen bond studied by ultrafast vibrational spectroscopy

Kozich

Dreyer

Ashihara

et al. 2006

The Journal of Chemical Physics

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The ultrafast relaxation of the excited O-H stretching vibration is studied by ultrafast infrared-pump/infrared-probe and infrared-pump/Raman-probe spectroscopy. We demonstrate a 200 fs lifetime of the hydrogen-bonded O-H stretching mode in 2-(2'-hydroxy-5'-methyl-phenyl)benzotriazole (TINUVIN P). O-H stretching relaxation occurs through a few major channels that all involve combination and overtone bands of modes with considerable in-plane O-H bending character. In particular, the mode, which contains the largest O-H bending contribution, plays a prominent role for primary processes of intramolecular vibrational energy redistribution. Theoretical calculations of vibrational energy transfer rates based on a Fermi golden rule approach account for the experimental findings.

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“…Note that Bakker derived a similar fluctuating Landau-Teller formula in a different manner [51]. It was successfully applied to molecular systems by Sibert and coworkers [52].…”

Section: B One-dimensional Relaxing Mode Coupled To a Fluctuating Bathmentioning

confidence: 99%

Non‐Markovian Theory of Vibrational Energy Relaxation and its Applications to Biomolecular Systems

Fujisaki

Zhang

Straub

2011

Advancing Theory for Kinetics and Dynamics of Complex, Many‐Dimensional Systems: Clusters and Proteins

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Vibrational relaxation in the condensed phase

Cited by 30 publications

References 22 publications

Vibrational dynamics and solvatochromism of the label SCN in various solvents and hemoglobin by time dependent IR and 2D-IR spectroscopy

Vibrational dynamics and solvatochromism of the label SCN in various solvents and hemoglobin by time dependent IR and 2D-IR spectroscopy

Mode-selective O–H stretching relaxation in a hydrogen bond studied by ultrafast vibrational spectroscopy

Non‐Markovian Theory of Vibrational Energy Relaxation and its Applications to Biomolecular Systems

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