TY - JOUR
T1 - Inverse deuterium isotope effect on radiationless electronic transitions
AU - Amirav, Aviv
AU - Sonnenschein, Mark
AU - Jortner, Joshua
N1 - Funding Information:
This physical picture provides a proper description for the disappearanceo f the deuterium isotope effect at high E, e 1500 cm-l), which is attributed to in-tersystemc rossing intermediated by a congestedm ani-fold of T, states.A t high values of Ev, the level structure of the intermediating TX statesb ecomes dense. Under these circumstances,t he coupling scheme( 9) correspondst o sequential decay via the {lT$} quasi-continuum_ This state of affairs is analogous to internal conversion between high statesi n the statistical limit [ 193. The decay rate, yH, of a high S1 vlbronic level is then roughly T = 2nW~op_X)w, here pX is the density of statesi n the TX manifold.~ is expected to be characterizedb y a small, normal, deuterium isotope effect, whereupon the inverse deuterium isotope effect is eroded at high Eva Traditional theories of intramolecular radiationless transitions [l] focused attention on the details of the final statesw ithin the dissipative quasicontinuum, which were segregatedin to promoting modes and accepting modes. The present work provides novel information concerning the characteristicso f intermediating statesi nvolved in intramolecular radiationless transitions_ This researchw as supported by the United States Amry through its European ResearchO ffice, and by the United States-Israel Binational Science Foundation, Jerusalem (Grant No. 2641).
PY - 1983/9/30
Y1 - 1983/9/30
N2 - Fluorescence quantum yields, Y, front photoselected vibrational states in the S1 manifold of anthracene and of perdeuterated anthracene in planar supersonic jets reveal a large inverse deuterium isotope effect on the non-radiative relaxation from the S1 origin (YH/YD = 5), while for high (≥1500 cm-1) excess energies above the S1 origin the inverse isotope effect is eroded (YH/YD ≈ 1). Novel information emerges on intermediating states involved in intersystem crossing.
AB - Fluorescence quantum yields, Y, front photoselected vibrational states in the S1 manifold of anthracene and of perdeuterated anthracene in planar supersonic jets reveal a large inverse deuterium isotope effect on the non-radiative relaxation from the S1 origin (YH/YD = 5), while for high (≥1500 cm-1) excess energies above the S1 origin the inverse isotope effect is eroded (YH/YD ≈ 1). Novel information emerges on intermediating states involved in intersystem crossing.
UR - http://www.scopus.com/inward/record.url?scp=0010843207&partnerID=8YFLogxK
U2 - 10.1016/0009-2614(83)87414-4
DO - 10.1016/0009-2614(83)87414-4
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AN - SCOPUS:0010843207
SN - 0009-2614
VL - 100
SP - 488
EP - 493
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 6
ER -