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Nuclear quantum effects in electronically adiabatic quantum time correlation functions: Application to the absorption spectrum of a hydrated electron
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10.1063/1.3173276
/content/aip/journal/jcp/131/2/10.1063/1.3173276
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/2/10.1063/1.3173276

Figures

Image of FIG. 1.
FIG. 1.

Normalized classical gap and transition dipole autocorrelation functions, and , respectively, for the first five electronic transitions . Solid line: , dashed: , dotted: , dashed-dotted: , dashed-dotted-dotted .

Image of FIG. 2.
FIG. 2.

The absorption spectrum of an equilibrium, ground state hydrated electron computed using the classical correlation functions, Eq. (16). The spectrum is normalized to unity at its maximum. The inset shows all computed spectral contributions to the high energy tail. The figure also includes the extrapolated spectrum (dashed) including the contributions from higher energy bands .

Image of FIG. 3.
FIG. 3.

The absorption bands of the highest seven computed transitions , with a fitted Lorentzian function to model the progression of the band maxima of higher energy delocalized states.

Image of FIG. 4.
FIG. 4.

Comparison of the absorption spectrum of an equilibrium, ground state hydrated electron computed using the classical correlation functions (solid line) to the experimental curve (dashed) (Ref. 21) and the previously published spectrum in the slow-modulation limit (dotted line) (Ref. 27). The figure also includes the extrapolated spectrum (dashed-dotted) including the contributions from higher energy bands .

Image of FIG. 5.
FIG. 5.

Fourier transforms of the gap (left) and the transition dipole autocorrelation functions (right) for the (upper panels) and transitions (lower panels). The dashed line corresponds to the classical function, while the solid line shows the quantized correlation functions using the harmonic quantization scheme. Note the different scales between the two frames showing the transition dipole autocorrelation functions.

Image of FIG. 6.
FIG. 6.

The absorption spectrum of an equilibrium, ground state hydrated electron computed using classical correlation functions (dashed-dotted) and the harmonic quantization scheme (Refs. 29 and 30) (dashed). The spectra are normalized to unity at their maximum. The experimental spectrum is shown for comparison (solid line) (Ref. 21). The absolute peak intensities [Eq. (12)] are 50.9 and 60.5 a.u. for the computed classical and the quantized spectra, 32.8 a.u. for the experiment (corresponding to the maximum molar absorption coefficient, ) (Ref. 42). The lower panel shows the calculated spectra linearly shifted to align the maximum with the experimental spectrum, 1.72 eV.

Tables

Generic image for table
Table I.

The initial value of the classical gap-gap and transition dipole moment autocorrelation functions, and their quantum/classical ratios.

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/content/aip/journal/jcp/131/2/10.1063/1.3173276
2009-07-14
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Nuclear quantum effects in electronically adiabatic quantum time correlation functions: Application to the absorption spectrum of a hydrated electron
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/2/10.1063/1.3173276
10.1063/1.3173276
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