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Photodissociation dynamics of 1-propanol and 2-propanol at 193.3 nm

Authors: Weidong Zhou; Yan Yuan; Jingsong Zhang;

Photodissociation dynamics of 1-propanol and 2-propanol at 193.3 nm

Abstract

193.3-nm photodissociation dynamics of jet-cooled 1-propanol and 2-propanol and their partially deuterated variants are examined by using the high-n Rydberg-atom time-of-flight technique. Isotope labeling studies show that O–H bond fission is the primary H-atom production channel in the ultraviolet photodissociation of both 1-propanol and 2-propanol. Center-of-mass (c.m.) product translational energy release of the RO–H dissociation channel is large, with 〈fT〉=0.78 for H+1-propoxy (n-propoxy) and 0.79 for H+2-propoxy (isoproxy). Maximum c.m. translational energy release yields an upper limit of the O–H bond dissociation energy: 433±2 kJ/mol in 1-propanol and 435±2 kJ/mol in 2-propanol. H-atom product angular distribution is anisotropic (with β≈−0.79 for 1-propanol and −0.77 for 2-propanol), suggesting an electronic transition moment perpendicular to the H–O–C plane and a short excited-state dissociation lifetime (less than a rotational period). Information about photodissociation dynamics and bond energies of the partially deuterated propanols are also obtained. The 193.3-nm photodissociation dynamics of 1-propanol and 2-propanol are nearly identical to each other and are similar to those of methanol and ethanol. This indicates a common RO–H dissociation mechanism: after the nO→σ*(O–H)/3s excitation localized on the H–O–C moiety, the H atom is ejected promptly in the H–O–C plane in a time scale shorter than a rotational period of the parent molecule, and it dissociates along the O–H coordinate on the repulsive excited-state potential-energy surface with a large translational energy release.

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
20
Average
Top 10%
Average
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