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Insights in quantum dynamical effects in the infrared spectroscopy of liquid water from a semiclassical study with an ab initio-based flexible and polarizable force field
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10.1063/1.3670960
/content/aip/journal/jcp/135/24/10.1063/1.3670960
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/24/10.1063/1.3670960

Figures

Image of FIG. 1.
FIG. 1.

The IR spectrum of the shifted 3D harmonic potential for the OH molecule. [The same scale for Panels (a) and (b).]

Image of FIG. 2.
FIG. 2.

The IR spectrum of the 3D Morse potential for the OH molecule. (a) Comparison of the LSC-IVR spectrum based on the Kubo-transformed dipole-derivative correlation function to that based on the standard version for T = 100 K. (b) Comparison of the LSC-IVR results at different temperatures. (c) Comparison of the classical results at different temperatures.

Image of FIG. 3.
FIG. 3.

Schematic representation of the simulation for the Morse potential. Red line illustrates the Morse potential while Blue line shows its harmonic approximation at the minimum of the well. (a) Classical MD trajectories contain no zero-point energy so the regime that the system can reach is controlled by the energy level on the order of k B T. They oscillate around the minimum of the well and predict almost results very close to the harmonic frequency, which are doomed to be blueshifted from the quantum results. (b) Trajectories in the LSC-IVR contain zero-point energy so the region that the system can access is much broader, accounting for the majority of anharmonicity of the potential surface. Because the zero-point energy is much larger than k B T, the LSC-IVR result is insensitive to the change of the temperature.

Image of FIG. 4.
FIG. 4.

Normalized dipole-derivative correlation functions for the 3D Morse potential for T = 100 K.

Image of FIG. 5.
FIG. 5.

The normalized local normal frequency distribution of liquid water at T = 300 K using the TTM3-F model. (Note ℏβ ∼ 208.5 cm−1.)

Image of FIG. 6.
FIG. 6.

Normalized dipole-derivative correlation functions for liquid water at T = 300 K using the TTM3-F model.

Image of FIG. 7.
FIG. 7.

Comparison of simulated IR spectra using the TTM3-F model to the experimental results.

Image of FIG. 8.
FIG. 8.

Comparison of simulated IR spectra in the librational regime.

Tables

Generic image for table
Table I.

Peak positions of the O–H stretching mode at different temperatures.

Generic image for table
Table II.

Peak positions of the O–H stretching mode estimated by different periods of the LSC-IVR correlation function (same for 100 K and 300 K).

Generic image for table
Table III.

Peak positions of the O–H stretching mode estimated with the Gaussian damping function with different t half parameters (same for 100 K and 300 K).

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/content/aip/journal/jcp/135/24/10.1063/1.3670960
2011-12-28
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Insights in quantum dynamical effects in the infrared spectroscopy of liquid water from a semiclassical study with an ab initio-based flexible and polarizable force field
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/24/10.1063/1.3670960
10.1063/1.3670960
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