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The calculated infrared spectrum of using a new full dimensional ab initio potential surface and dipole moment surface
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Image of FIG. 1.
FIG. 1.

Sketch of one-dimensional potential energy cut along the isomerization path with corresponding geometries. I, II, and III define the grid regions as described in the text. Ab initio barrier height of the transition state is .

Image of FIG. 2.
FIG. 2.

Potential energy cuts along each normal mode (mass scaled). Mode numbering corresponds to increasing harmonic frequency (given in Table I). Insets are pictures of the corresponding modes.

Image of FIG. 3.
FIG. 3.

Root mean square (rms) fitting error as a function of data cutoff energy.

Image of FIG. 4.
FIG. 4.

Contour plot of the potential energy surface for with fixed at the asymmetric equilibrium configuration of the global minimum in the variables and the planar rotation angle . equals 0 when the vector bisects the HOH bond angle and is positive as moves in the direction of the ionic H and negative when moves toward the free H.

Image of FIG. 5.
FIG. 5.

Cuts of dipole moment components for normal modes against mass-weighted normal mode coordinates . Note that only mode 3 has a nonzero component.

Image of FIG. 6.
FIG. 6.

Convergence of six fundamental energies, obtained by CI calculations, as a function of the -mode representation of the potential mode coupling for where represents the number of modes being coupled.

Image of FIG. 7.
FIG. 7.

Experimental (Ref. 4) and calculated IR spectra of in the low-frequency portion of the experimental spectrum. Intensity is given in arbitrary units and is normalized to the intensity of the band.

Image of FIG. 8.
FIG. 8.

Wave function contour plots of the and states as functions of the normal and and and .

Image of FIG. 9.
FIG. 9.

Cuts of , , and components of the dipole with respect to the out-of-plane normal coordinate for the indicated fixed values of , the ionic OH stretch normal mode.

Image of FIG. 10.
FIG. 10.

High-frequency range of the IR spectrum for both experiment (Refs. 4 and 36) and theory. Intensity is given in arbitrary units and is normalized to the intensity of the band. The low-intensity bands have been blown up as an inset in the theoretical spectrum.

Image of FIG. 11.
FIG. 11.

IR spectra of isotopologs indicated, where notation indicates the is immediately followed by the ionic H/D. Intensities are normalized to the absolute intensity of the band.


Generic image for table
Table I.

Comparison of vibrational frequencies (in ) for fundamentals and various overtones and combination bands of from the present calculations, denoted PES-CI, previous calculations, as indicated and described in detail in the text, and experiment. Also shown are the harmonic frequencies (HO) directly from ab initio calculations and the fitted potential energy surface.

Generic image for table
Table II.

Band frequencies (in ) and intensities (arbitrary units) and normalized intensities from the present CI calculations. Assignment is based on the CI eigenvectors obtained from the diagonalization of the Hamiltonian matrix in the basis of virtual states.

Generic image for table
Table III.

Vibrational frequencies in and intensities in arbitrary units of IR spectral bands for and isotopologs indicated.


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: The calculated infrared spectrum of Cl−H2O using a new full dimensional ab initio potential surface and dipole moment surface