Predissociation and Vibrational Relaxation in the B State of I2 in a Kr MatrixClick to copy article linkArticle link copied!
Abstract
An apparent predissociation rate kpre of 0.06 ps-1 at 10 K which rises to 0.11 ps-1 at 40 K is observed in pump−probe spectra of the population arriving in predissociated states. We show that the observed rate is determined by a balance of the calculated energy-dependent predissociation rate kp(E), which rises in approaching the relevant curve crossing from higher energies, and the vibrational relaxation rate kvib, which funnels population toward this crossing. kvib is explored via several probe windows using fluorescence emitted by three different ionic states. kvib increases exponentially with energy above the B state potential minimum. Predissociation occurs in a region where kvib equals kp. The increase of kvib with matrix temperature T explains the rise of kpre at 40 K. Disorder induced by double doping furthermore increases kvib. The deduced effective curve crossing matrix element of 15−20 cm-1 is in accordance with calculations.
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To whom correspondence should be addressed. E-mail: nikolaus. [email protected].
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