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Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view
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10.1063/1.4829679
/content/aip/journal/jcp/139/20/10.1063/1.4829679
http://aip.metastore.ingenta.com/content/aip/journal/jcp/139/20/10.1063/1.4829679

Figures

Image of FIG. 1.
FIG. 1.

Radial distribution functions of SPC/E models at = 300 K and ρ = 1 g/cm3: (a) (), (b) (), and (c) (). The solid lines are for the rigid model. The dashed and dotted-dashed lines are for and of flexible molecules, respectively.

Image of FIG. 2.
FIG. 2.

Asphericity distribution of SPC/E model. The solid line is for the rigid model. The dashed and dotted-dashed lines are for and , respectively. By the dot vertical lines at = 1.46, 1.72, and 1.98, the distribution of each model is divided into four regions, with each corresponding to a VG.

Image of FIG. 3.
FIG. 3.

Radial distribution functions of the four VGs for : (a) (), (b) (), and (c) (). In each panel, the solid, dotted, dashed, and dotted-dashed lines are for VG I, II, III, and IV, respectively.

Image of FIG. 4.
FIG. 4.

Distribution of H-bond configuration for molecules in each VG of . For a VG, the distribution is presented by bars with the same symbol and color, with the bars summed to be a unit. The distribution of each VG is shown for nine H-bond configurations, with the fraction of D3A2 almost zero for all VGs.

Image of FIG. 5.
FIG. 5.

INM DOS, (ω), and its atomic contributions, (ω), for (a) and (b) at T = 300 K and ρ = 1 g/cm3. The black solid lines are for the INM DOS. The red dashed and blue dotted-dashed lines are for the H- and O-atom contributions, respectively. The inset in (a) shows the comparison of the intermolecular and unstable branches calculated for (black-solid line) with those of the rigid model 46 (green dashed line) at the same density and temperature, where both curves are normalized.

Image of FIG. 6.
FIG. 6.

Stable INM spectrum of (ω) and the atomic power spectrum (ω) for : (a) O atom and (b) H atom. In each panel, the solid line is for the stable branch of (ω) and the dash line is for (ω) obtained via the VACF () shown in the inset, with both curves normalized. In an inset in (a), the bending and stretching portions of the O-atom contribution are enlarged for a clear view.

Image of FIG. 7.
FIG. 7.

The same as in Fig. 6 , except for .

Image of FIG. 8.
FIG. 8.

IPRs of in (left column) and (right column). In each panel, the red solid, green dotted-dashed, and blue dashed lines are the calculated results of (), (), and (), respectively. For each column, the three panels from top to bottom are for the intermolecular and unstable, the bending, and the stretching INMs.

Image of FIG. 9.
FIG. 9.

Average number () of involved OH bond in each molecule participated in with ω. The average number is obtained by Eq. (19) evaluated at frequencies where (ω) is larger than 10−6 cm. The red circles and black squares are the results calculated for and respectively.

Image of FIG. 10.
FIG. 10.

H-atom contribution to the bending and stretching bands calculated for the four VGs: (a) and (b) . In each panel, the solid, dotted, dashed, and dotted-dashed lines are the results calculated for VG I, II, III, and IV, respectively.

Image of FIG. 11.
FIG. 11.

H-atom contribution to the bending band calculated for subensembles of H-bond configuration: (left column) and (right column). In each column, the panels from top to bottom are for H-bond configurations with two, one, or zero donated H-bonds. In all panels, the dotted, solid, dashed, and dotted-dashed lines indicate the results of H-bond configurations with three, two, one, and zero accepted H-bonds, respectively.

Image of FIG. 12.
FIG. 12.

H-atom contribution to the stretching band calculated for subensembles of H-bond configuration: (left column) and (right column). In each column, the panels from top to bottom are for H-bond configurations with total H-bond number from 5 to 1. For = 5 or 4, there is only one possible H-bond configuration. For = 3, 2, or 1, the solid, dashed, and dotted-dashed lines are for the configurations with two, one, or zero accepted H-bonds, respectively.

Image of FIG. 13.
FIG. 13.

Average bending frequency ω versus the total H-bond number of a configuration: (a) (left panel) and (b) (right panel). The circles, squares, diamonds, and triangles are for the configurations with from zero to three, respectively. The solid lines from left to right are the linear fit for each data set with = 0, 1, or 2; the dash lines from top to bottom are the linear fit for the data set with = 2, 1 or 0, respectively.

Image of FIG. 14.
FIG. 14.

Average stretching frequency ω versus the total H-bond number of a configuration. The rest are the same as in Fig. 13 , except that the dash lines from top to bottom are the linear fit for the data set with = 0, 1 or 2, respectively.

Tables

Generic image for table
Table I.

Parameters in intramolecular interactions of and . The values of the parameters in and are referred from Refs. 52 and 58 , respectively, except for the value being reduced to one quarter of the referred data. The force constants , , , and are in the unit of kJ mol−1 Å−2 and the unit of is kJ mol−1 rad−2.

Generic image for table
Table II.

Average molecular fractions of subensembles for and . The subensembles are either four VGs or ten H-bond configurations. For each kind of classification, the fractions of all subensembles are summed to be unit. For H-bond configurations, the results are evaluated with the H-bond definition of both energetic and OOH-angle criterions described in the text and the results evaluated with the energetic criterion only are given in the parentheses.

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/content/aip/journal/jcp/139/20/10.1063/1.4829679
2013-11-27
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view
http://aip.metastore.ingenta.com/content/aip/journal/jcp/139/20/10.1063/1.4829679
10.1063/1.4829679
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