E-T and near-resonant E-V energy transfer in the quenching of the 1. 0 and 2. 3. mu. m electronically excited states of PuF/sub 6/ by H/sub 2/ and D/sub 2/

Journal Article · Tue Jan 01 04:00:00 EST 1985 · J. Chem. Phys.; (United States)

OSTI ID:5987577

Rice, W W; Barefield, II, J E; Pack, R T; Dye, B A

The quenching and energy transfer of electronically excited PuF/sub 6/ by H/sub 2/ and D/sub 2/ have been measured using laser-induced fluorescence (LIF) from both the 1.0 and 2.3 ..mu..m emitting states of PuF/sub 6/. Linear Stern--Volmer plots of the single exponential decay data give quenching rate constants (all in units of cm/sup 3/ molecule/sup -1/ s/sup -1/) for D/sub 2/ of (3.7 +- 1.7) x 10/sup -15/ and (8.7 +- 0.3) x 10/sup -16/ for the 1.0 and and 2.3 ..mu..m states, respectively, and a H/sub 2/ quenching rate constant of (4.8 +- 0.3) x 10/sup -14/ for the 1 ..mu..m LIF. The 2.3 ..mu..m LIF in H/sub 2/ is not a single exponential decay but a rapid decay followed by an anomalously long tail, which implies almost resonant Earrow-right-leftV energy transfer and storage. Kinetic modeling yields the following new rate constants: m PuF/sub 6/*+H/sub 2/..-->..PuF/sub 6/+H/sup not-equal//sub 2/, k = (2.05 +- 0.30) x 10/sup -14/; P H/sub 2//sup not-equal/+PuF/sub 6/..-->..H/sub 2/+PuF/sub 6/*, k = (3.1 +- 0.5) x 10/sup -14/; H PuF/sub 6/*+H/sub 2/..-->..PuF/sub 6/+H/sub 2/, k = (3.1 +- 2.0) x 10/sup -15/; P H/sub 2//sup not-equal/+PuF/sub 6/..-->..H/sub 2/+PuF/sub 6/, k = (3.1 +- 3.0) x 10/sup -15/; H where PuF/sub 6/* is the 2.3 ..mu..m emitting electronically excited state of PuF/sub 6/ and H/sub 2//sup not-equal/ is vibrationally excited H/sub 2/ in the v = 1 state.

• Research Organization: University of California, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
• OSTI ID: 5987577
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 82:1; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640304* -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
ACTINIDE COMPOUNDS
COLLISIONS
DE-EXCITATION
DEUTERIUM
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
FLUORESCENCE
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDROGEN
HYDROGEN ISOTOPES
ISOTOPES
KINETICS
LIGHT NUCLEI
LUMINESCENCE
MOLECULE COLLISIONS
MOLECULE-MOLECULE COLLISIONS
NONMETALS
NUCLEI
ODD-ODD NUCLEI
PLUTONIUM COMPOUNDS
PLUTONIUM FLUORIDES
RADIATIONLESS DECAY
STABLE ISOTOPES
TRANSURANIUM COMPOUNDS