2D IR spectra of cyanide in water investigated by molecular dynamics simulations

Title
2D IR spectra of cyanide in water investigated by molecular dynamics simulations
Author(s)
이명원Carr, Joshua K.[Carr, Joshua K.]Goellner, Michael[Goellner, Michael]Hamm, Peter[Hamm, Peter]Meuwly, Markus[Meuwly, Markus]
Keywords
ULTRAFAST INFRARED-SPECTROSCOPY; VIBRATIONAL-ENERGY RELAXATION; HYDROGEN-BOND DYNAMICS; ECHO CORRELATION SPECTROSCOPY; 2-DIMENSIONAL OPTICAL SPECTROSCOPY; LIQUID WATER; AQUEOUS-SOLUTION; AMYLOID FIBRILS; LIGAND DYNAMICS; CARBON-MONOXIDE
Issue Date
201308
Publisher
AMER INST PHYSICS
Citation
JOURNAL OF CHEMICAL PHYSICS, v.139, no.5
Abstract
Using classical molecular dynamics simulations, the 2D infrared (IR) spectroscopy of CN- solvated in D2O is investigated. Depending on the force field parametrizations, most of which are based on multipolar interactions for the CN- molecule, the frequency-frequency correlation function and observables computed from it differ. Most notably, models based on multipoles for CN- and TIP3P for water yield quantitatively correct results when compared with experiments. Furthermore, the recent finding that T-1 times are sensitive to the van der Waals ranges on the CN- is confirmed in the present study. For the linear IR spectrum, the best model reproduces the full widths at half maximum almost quantitatively (13.0 cm(-1) vs. 14.9 cm(-1)) if the rotational contribution to the linewidth is included. Without the rotational contribution, the lines are too narrow by about a factor of two, which agrees with Raman and IR experiments. The computed and experimental tilt angles (or nodal slopes) alpha as a function of the 2D IR waiting time compare favorably with the measured ones and the frequency fluctuation correlation function is invariably found to contain three time scales: a sub-ps, 1 ps, and one on the 10-ps time scale. These time scales are discussed in terms of the structural dynamics of the surrounding solvent and it is found that the longest time scale (approximate to 10 ps) most likely corresponds to solvent exchange between the first and second solvation shell, in agreement with interpretations from nuclear magnetic resonance measurements. (C) 2013 AIP Publishing LLC.
URI
http://hdl.handle.net/YU.REPOSITORY/29232http://dx.doi.org/10.1063/1.4815969
ISSN
0021-9606
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