2D IR spectra of cyanide in water investigated by molecular dynamics simulations
Journal of Chemical Physics
By: Myung Won Lee, Joshua K. Carr, Michael Gollner, Peter Hamm, and Markus Meuwly
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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) α 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 (≈10 ps) most likely corresponds to solvent exchange between the first and second solvation shell, in agreement with interpretations from nuclear magnetic resonance measurements.
Suggested Citation
Lee, M.W., Carr, J.K., Gollner, M., Hamm, P., Meuwly, M., 2013, 2D IR spectra of cyanide in water investigated by molecular dynamics simulations: Journal of Chemical Physics, v. 139, no. 5, p. 1-12, https://doi.org/10.1063/1.4815969.
| Publication type | Article |
|---|---|
| Publication Subtype | Journal Article |
| Title | 2D IR spectra of cyanide in water investigated by molecular dynamics simulations |
| Series title | Journal of Chemical Physics |
| DOI | 10.1063/1.4815969 |
| Volume | 139 |
| Issue | 5 |
| Publication Date | August 02, 2013 |
| Year Published | 2013 |
| Language | English |
| Publisher | American Institute of Physics |
| Publisher location | New York, NY |
| Description | 13 p. |
| Larger Work Type | Article |
| Larger Work Subtype | Journal Article |
| Larger Work Title | Journal of Chemical Physics |
| First page | 1 |
| Last page | 12 |