000063713 001__ 63713
000063713 005__ 20190527112159.0
000063713 0247_ $$2doi$$a10.1063/1.481502
000063713 02470 $$2ISI$$a000086851200019
000063713 037__ $$aARTICLE
000063713 245__ $$aDouble-resonance overtone photofragment spectroscopy of trans-HONO. I. Spectroscopy and intramolecular dynamics
000063713 269__ $$a2000
000063713 260__ $$c2000
000063713 336__ $$aJournal Articles
000063713 520__ $$aUsing the technique of double-resonance overtone photofragment spectroscopy (DROPS), we have measured rotationally resolved vibrational overtone transitions to the previously unobserved 5v(1), 6v(1), and 7v(1) levels of gas-phase trans-nitrous acid (HONO) in its electronic ground state. Observing the onset of dissociation from different rovibrational states of 5v(1) near threshold determines the HO-NO bond energy to be D-0=16 772 +/- 14 cm(-1). Observed spectral splittings and broadening of individual rovibrational transitions provide quantitative data on the rate and extent of collision free vibrational energy redistribution that would result after coherent ultrashort pulse excitation. In parallel with these frequency domain measurements, we determine the unimolecular dissociation rates directly in time for trans-HONO molecules excited to several rotational states near threshold. The combination of time- and frequency-resolved data allows us to estimate the linewidth contributions from the finite dissociation lifetime of the molecule. Our results reveal intramolecular dynamics that are clearly not a simple function of the vibrational energy but rather depend sensitively upon specific couplings and, in turn, on the vibrational character of the individual states excited. (C) 2000 American Institute of Physics. [S0021-9606(00)00320-2].
000063713 700__ $$aReiche, F
000063713 700__ $$aAbel, B
000063713 700__ $$0242819$$g109138$$aBeck, Rainer D
000063713 700__ $$aRizzo, T R$$g106239$$0242829
000063713 773__ $$j112$$tJournal of Chemical Physics$$k20$$q8885-8898
000063713 909C0 $$xU10106$$0252096$$pLCPM
000063713 909CO $$pSB$$particle$$ooai:infoscience.tind.io:63713
000063713 937__ $$aLCPM-ARTICLE-2000-002
000063713 970__ $$aISI:000086851200019/LCPM
000063713 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000063713 980__ $$aARTICLE