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Vibronically induced decay paths from the 1B1-state of water and its isotopomers
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10.1063/1.4794158
/content/aip/journal/jcp/138/10/10.1063/1.4794158
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/10/10.1063/1.4794158
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

Total kinetic energy release spectra via excitation to the 000 rotational level of the -state of HOD leading (a) to D+OH and (b) to H+OD, with combs indicating vibration assignments of the X2Π products.

Image of FIG. 2.
FIG. 2.

Vibrational populations of (a) OH(X2Π) and (b) OD(X2Π), following dissociation of HOD excited via low lying rotational levels of its -state.

Image of FIG. 3.
FIG. 3.

Potential energy surfaces for (a) 1B1, (b) 1A2, and (c) 1B1, with a fixed ∠HOH = 104.5°. The contour lines are at multiples of 4000 cm−1 relative to the potential minimum for 1A1 and are labelled in multiples of 1000 cm−1, with an upper cut-off at 100 000 cm−1.

Image of FIG. 4.
FIG. 4.

The coordinate dependant T mn coupling matrix elements of (∂/∂r 1 + ∂/∂r 2). Blue and red contour lines are for positive and negative amplitudes, respectively. (a) T 12 1A2, peaks at ±2.1 Å−1, contour interval 0.05 Å−1. (b) T 13 , peak at +5.2 Å−1, interval 0.05 Å−1, and (c) T 23 1A2 , peaks at ±15.5 Å−1, interval 0.1Å−1. The bold features near r min = 0.7 Å are truncation artefacts at the inner edges of the data set, and are masked out for use in the dynamics calculations.

Image of FIG. 5.
FIG. 5.

An apparent avoided crossing of the 1A2 and surfaces for r mean = 1.75 Å as a function of (r 1 –r 2 ), i.e., the anti-symmetric stretching coordinate. The minimum separation for this value of r mean is 6500 cm−1.

Image of FIG. 6.
FIG. 6.

Experimental and calculated population distributions for OH(X,2Π,v) products from pre-dissociation of (a) the 000 level of the H2O( ) state, and (b) the 000 and 101 levels of the HOD( ) state. The calculated distributions for the and 1A2 decay paths are each normalised to a sum of 100, as are the similarly normalised experimental distributions.

Image of FIG. 7.
FIG. 7.

Population distributions for OD(X,2Π,v) products, as in Figure 6 , for the 000 and 101 levels of (a) the D2O( ) state, and (b) the HOD( ) state.

Image of FIG. 8.
FIG. 8.

The calculated outgoing wavepacket on the 1A2 surface following excitation of HOD, in Jacobi coordinates with R = D–OHcm and r = O–H, superimposed on contour lines for the potential (Fig. 3(b) ).

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/content/aip/journal/jcp/138/10/10.1063/1.4794158
2013-03-11
2014-04-25
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Vibronically induced decay paths from the C̃1B1-state of water and its isotopomers
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/10/10.1063/1.4794158
10.1063/1.4794158
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