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Real-time observation of intramolecular proton transfer in the electronic ground state of chloromalonaldehyde: An ab initio study of time-resolved photoelectron spectra
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10.1063/1.2432119
/content/aip/journal/jcp/126/5/10.1063/1.2432119
http://aip.metastore.ingenta.com/content/aip/journal/jcp/126/5/10.1063/1.2432119

Figures

Image of FIG. 1.
FIG. 1.

The pump-dump-probe scheme for chloromalonaldehyde. A linearly polarized pulse of frequency pumps a wave packet from the ground electronic state to an excited state, where it is dumped by a time-delayed pulse of frequency and subsequently probed by a third time-delayed pulse of frequency .

Image of FIG. 2.
FIG. 2.

Intramolecular proton transfer in the ground state of chloromalonaldehyde. Structure (a) is the most stable (global minimum), (b) is the transition state, and (c) is the secondary minimum. The frame of reference for the reaction coordinates is shown in structure (b).

Image of FIG. 3.
FIG. 3.

Potential energy surfaces for the ground state (lower panel), excited state (central panel), and ion state (upper panel) of chloromalonaldehyde. All potential surfaces were calculated at the classically averaged geometry of the ground state.

Image of FIG. 4.
FIG. 4.

Panel (a): time evolution of the population in the ground state (, thick solid line) and excited state (, thin solid line) for scheme B in Table II [the time origin is the center of the pump pulse in panels (a) and (b)]. The decomposition of into the component (, short-dashed line) and vibrationally hot components (, long-dashed line) is also shown. Panel (b): time evolution of for schemes A (thick solid line), B (thin solid line), C (long-dashed line), and D (short-dashed line). Panel (c): decomposition of the final vibrationally hot population into the vibrational eigenstates of the ground state for schemes A–D.

Image of FIG. 5.
FIG. 5.

Contour plots of selected vibrational eigenstates of the electronic ground state. In all panels, the contour of the ground state potential surface at the transition state energy is also shown (thickest solid lines).

Image of FIG. 6.
FIG. 6.

Contour plots of the photoionization intensity defined in Eq. (21) (arbitrary units). Panel (a): component. (dotted line), 9 (short-dashed line), 11 (thin solid line), and 13 (long-dashed line). Panel (b): component. (dotted line), 0.50 (short-dashed line), 4 (thin solid line), 20 (long-dashed line), and 60 (thick solid line). In both panels, contour plots of the ground state potential at 0.25, 0.936, and are also shown (thick solid lines).

Image of FIG. 7.
FIG. 7.

Time evolution of integrated photoelectron signals in arbitrary units (scales to the right) obtained with schemes A (upper panel) and C (lower panel). Thick solid lines: calculation employing ab initio matrix elements with perpendicular orientation ( component, see text), thin solid lines: calculation employing ab initio matrix elements with parallel orientation ( component), and dashed line: Condon-approximation calculation. For the sake of presentation the curves have been vertically shifted but only the results obtained with perpendicular orientation have been rescaled as indicated (factors of 0.27 and 0.30 for schemes A and C, respectively). In both panels, the vibrationally hot left-ratio population in the ground state is also shown (thin solid lines, scales to the left).

Image of FIG. 8.
FIG. 8.

Time evolution of integrated photoelectron signals in arbitrary units (scales to the right) obtained with schemes A (upper panel) and B (lower panel) for probe pulse widths of (dashed lines), (thin solid lines), and (thick solid lines). For the sake of presentation the curves have been vertically shifted but not rescaled. In both panels, the lower thin solid line is the vibrationally hot left-ratio population in the ground state (scales to the left).

Image of FIG. 9.
FIG. 9.

Same as in Fig. 8 but for schemes C (upper panel) and D (lower panel).

Image of FIG. 10.
FIG. 10.

Panel (a): photoelectron kinetic energy distributions for scheme B with and , 225, and . Panel (b): decomposition of the ground state wave packets into vibrational eigenstates of the ion surface. The component was projected out in all cases, and the peaks were shifted to classical kinetic energies, according to Eq. (24). Panel (c): Contour plots of the vibrationally hot population in the ground state surface at , 225, and . The contour of the ground state potential surface at the transition state energy is also shown (thickest solid lines).

Image of FIG. 11.
FIG. 11.

Contour plots of selected vibrational eigenstates of the ion state. In all panels, the contour of the ground state potential surface at the transition state energy is shown (thickest solid lines) to facilitate comparison with Figs. 5 and 10.

Tables

Generic image for table
Table I.

Vibrational spectra for the ground and excited electronic states (eV) and their Franck-Condon factors. The vibrational levels of the ground and excited states are shown along columns and rows, respectively.

Generic image for table
Table II.

Parameters of different pump-dump schemes. Intensities are given in , frequencies in eV, widths (FWHM) in fs, and time delays in fs. The final vibrationally hot population in the ground state is also given.

Generic image for table
Table III.

Partial wave components of the outermost occupied orbital of chloromalonaldehyde, where and are, respectively, the angular momentum and its projection on the quantization axis of the molecular frame (, perpendicular to the molecular plane in Fig. 2). Left basin and right basin correspond to (, and (, , respectively.

Generic image for table
Table IV.

Resonant peaks in the partial photoionization cross sections ( component) along the direction of the reaction configuration space (the proton moves from the left to the right as increases). Energy and height indicate the positions and heights of the partial cross section peaks, respectively.

Generic image for table
Table V.

Absolute values of partial wave components of the photoionization matrix elements, where and are, respectively, the angular momentum and its projection on the quantization axis of the molecular frame (, perpendicular to the molecular plane in Fig. 2). Left basin, barrier, and right basin correspond to (, , (, , and (, , respectively.

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/content/aip/journal/jcp/126/5/10.1063/1.2432119
2007-02-02
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Real-time observation of intramolecular proton transfer in the electronic ground state of chloromalonaldehyde: An ab initio study of time-resolved photoelectron spectra
http://aip.metastore.ingenta.com/content/aip/journal/jcp/126/5/10.1063/1.2432119
10.1063/1.2432119
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