Vibrational energy relaxation of the cyanide ion in aqueous solution

Heilweil, Edwin J.; Doany, F. E.; Moore, Robert C.; Hochstrasser, Robin M.

doi:10.1063/1.442869

Cited by 111 publications

(81 citation statements)

References 25 publications

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“…Most commonly used force fields are based on functions for bonded interactions (bonds r and valence angles θ) and functions for torsions φ to describe the total energy as a function of geom (1) Here E v (t) is the vibrational energy at time 't', T 1 is the vibrational relaxation time and the overbar represents an average over non-equilibrium trajectories.…”

Section: Vibrational Relaxationmentioning

confidence: 99%

“…2). [1,2,20] The intermolecular interactions are treated with distributed multipoles and relaxation was found to depend sensitively on the van der Waals parameters. The fundamental insight that can be gained from such simulations concerns the mechanism for vibrational relaxation, i.e.…”

Section: Vibrational Relaxationmentioning

confidence: 99%

“…cyanide (CN − ) in water. [1,2] Although time scales of vibrational relaxation can be reliably measured using modern laser techniques, understanding the relaxation mechanism in molecular detail is much more difficult as it includes coupling and energy transfer to solvent modes. Another example is allostery which is the regulation of a protein by binding a small molecule at the allosteric site.…”

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Computational Spectroscopy and Reaction Dynamics

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Lütz²,

Lee³

et al. 2011

Chimia

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Physico- and bio-chemical processes on the femto- to picosecond time scale are ideally suited to be investigated with all-atom simulations. They include, amongst others, vibrational relaxation, ligand migration in sterically demanding environments (proteins, ices), or vibrational spectra. By comparing with experimental data, the results can be used to obtain an understanding of the mechanisms underlying the observations. Furthermore, most of these processes are sensitive to the intermolecular interactions. Therefore, detailed refinement of such interaction potentials is possible. Keywords: Computational spectroscopy · Molecular dynamics simulations · Reaction dynamicsThe classification of fast and ultrafast time scales in atoms and molecules depends to some extent on the process and property considered. For example, the electronic degrees of freedom change on considerably more rapid time scales than the nuclear motions. This is the basis of the Born-Oppenheimer approximation which is valid in many cases. In proteins, on the other hand, vibrations are much more rapid than changes in the secondary structure. Typical time scales for electronic motion in molecules are attoseconds, whereas vibrations are associated with femto-and pico-second time scales. In the following, ultrafast time scales in molecular systems -which are at the focus of the NCCR Molecular and Ultrafast Science and Technology (MUST) -will be associated with atto-to picosecond processes.Understanding ultrafast processes in molecular systems requires multi-faceted approaches, including experiment, theory and computation. A typical example is the vibrational relaxation of a solvated diatomic molecule, e.g. cyanide (CN − ) in water. [1,2] Although time scales of vibrational relaxation can be reliably measured using modern laser techniques, understanding the relaxation mechanism in molecular detail is much more difficult as it includes coupling and energy transfer to solvent modes. Another example is allostery which is the regulation of a protein by binding a small molecule at the allosteric site. An allosteric activator will enhance the activity of the protein. The most widely known but still incompletely understood allosteric protein is hemoglobin. Here, four binding sites for the ligand (O 2 ) exist. Binding of the first O 2 molecule increases the protein's affinity for binding the second O 2 molecule, etc. However, the molecular details underlying the enhanced affinity for subsequent O 2 ligands is still unexplained. Finally, one purpose of high-resolution spectroscopy is to understand the bonding pattern and geometrical details of a molecule by recording and analyzing spectroscopic signatures. As the size of the molecule grows, directly determining the structure of the molecule from the spectroscopic data becomes increasingly difficult. Even more difficult is the situation in proteins where spectroscopic features of small probe molecules such as CO or NO can be recorded but the splitting patterns of the vibrational spectra are difficult ...

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Section: Vibrational Relaxationmentioning

confidence: 99%

Section: Vibrational Relaxationmentioning

confidence: 99%

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Computational Spectroscopy and Reaction Dynamics

Cazade

Lütz²,

Lee³

et al. 2011

Chimia

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“…When Ted discovered the stimulated Raman gain from an aqueous potassium cyanide solution, we were able to use its time dependence to measure a vibrational relaxation time for the isolated CN of vibrational energy in such a short time? We had guessed that the Coulomb interactions were responsible but had no quantitative description (51). When this measurement was repeated 15 years later using stable tunable femtosecond IR pulses based on a titanium sapphire laser and an optical parametric amplifier (52), I called Ted and told him that his earlier measurement was right on the mark, but of course he was not surprised.…”

Section: Picosecond To Femtosecond Processesmentioning

confidence: 99%

On a Research Rollercoaster With Friends

Hochstrasser

2006

Annu. Rev. Phys. Chem.

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“…To understand vibrational energy flow on a more fundamental level, Robin studied the ultrafast vibrational energy relaxation in small molecules and ions, work which has had lasting influence on the experimental and theoretical growth of this field [196,299]. Jeffrey Owrutsky and Ted Heilweil were the PhD students responsible for that work, and report on a related problem in their paper.…”

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confidence: 99%