Intermediate-sized deuterium effect on T/sub 1/. -->. S/sub 0/ intersystem crossing in acetaldehyde

Journal Article · Thu Aug 02 04:00:00 EDT 1984 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j150660a013· OSTI ID:6455503

Beck, W F; Schuh, M D; Thomas, M P; Trout, T J

Reciprocal lifetimes, extrapolated to zero pressure, and rate constants for self-quenching have been measured for flash-excited T/sub 1/-state acetaldehyde and its deuterated analogues. Both reciprocal lifetimes and rate constants decrease with increasing deuteration and the ranges of values for these two are 3400-29,000 s/sup -1/ and 0.52 x 10/sup 7/-1.8 x 10/sup 7/ M/sup -1/ s/sup -1/. Reductions in reciprocal lifetimes and rate constants are very specific with respect to which hydrogens are deuterated, and the largest deuterium effect is found for the aldehyde hydrogen. The deuterium effect for acetaldehyde is intermediate in value between those for formaldehyde and larger ketones and aldehydes. Experimental evidence is presented in support of the activity of the out-of-plane deformation mode, nu/sub 14/, as the dominant accepting mode for T/sub 1/ ..-->.. S/sub 0/ intersystem crossing.

• Research Organization: Davidson Coll., NC
• OSTI ID: 6455503
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 88:16; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ACETALDEHYDE
ALDEHYDES
DATA
DEUTERIUM
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXPERIMENTAL DATA
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
STABLE ISOTOPES