Photoelectric Emission from Donor-Acceptor Solids and Donor Molecules

Batley, Michael; Lyons, L. E.

doi:10.1080/15421406808083451

Cited by 41 publications

(5 citation statements)

References 27 publications

(2 reference statements)

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“…The DFT/MRCI calculations find the adiabatic T 2 state to be located energetically about 500 cm À 1 above the S 1 minimum in the gas phase (Table 1), in good agreement with experimental observations [1,2,27] and advanced quantum chemical calculations. [39] Due to the high degree of ππ* and nπ* mixture in the triplet manifold, SOC is large between S 1 and T 1 as well as between S 1 and T 2 (Table 2).…”

Section: Chemphotochemsupporting

confidence: 83%

Modulation of Intersystem Crossing by Chemical Composition and Solvent Effects: Benzophenone, Anthrone and Fluorenone

Metz

Marian

2022

ChemPhotoChem

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Combined density functional theory and multireference configuration interaction methods including spin‐orbit coupling and spin‐vibronic interactions have been used to elucidate the photophysical pathways of benzophenone (BP), anthrone (A) and fluorenone (FL). Our results reveal that the slower S1(1nπ*) T1(3ππ*) passage of FL in the gas phase, as compared to BP and A, originates from the different electronic structures of the T1(3ππ*) states in these compounds and is not related to the planarity of the nuclear arrangement. Temperature eﬀects on the rate constants of intersystem‐crossing (ISC), reverse ISC (rISC) and fluorescence have been investigated for FL in solvents of diﬀerent polarity. Experimentally observed trends for rate constants are well reproduced. A nearly temperature‐ and solvent‐independent, slower down‐hill ISC component is attributed to the El‐Sayed‐forbidden S1(1ππ*) T1(3ππ*) transition in these environments. The faster El‐Sayed‐allowed S1(1ππ*) T2(3nπ*) ISC requires thermal activation in tetrahydrofuran and acetonitrile solution so that fluorescence may compete against triplet formation. In cyclohexane solution, S1(1ππ*) and T2(3nπ*) are nearly degenerate according to our calculations. Hence S1 T2 ISC and S1 T2 rISC have similar rate constants. If T2 T1 internal conversion could be slowed down by deuteration or perfluorination, for example, FL‐derivatives might show delayed fluorescence.

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Section: Chemphotochemsupporting

confidence: 83%

Modulation of Intersystem Crossing by Chemical Composition and Solvent Effects: Benzophenone, Anthrone and Fluorenone

Metz

Marian

2022

ChemPhotoChem

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“…If a monolayer is placed between the two Fig. 1 Some one-electron donors D (1-4) with their first gas-phase ionization potentials I D (6.25 eV for N,N,N 0 ,N 0 -tetramethyl-para-phenylenediamine (TMPD, 1), 71 6.83 eV for tetrathiafulvalene (TTF, 2), 72 7.6 eV for bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF, 3), 73 9.38 eV for benzene (4)) 74,75 some one-electron acceptors A (5-8) with their gasphase electron affinities A A (1.9 eV for para-benzoquinone (BQ, 5), 76 2.6 to 2.8 eV for buckminsterfullerene (C 60 , 6), 77 2.8 eV for 7,7,8,8-tetracyanoquinodimethane (TCNQ, 7), 78 then corrected to 3.3 eV, 79 3.13 eV for 2,3-chloro-5,6-dicyano-para-benzoquinone (DDQ, 8)), 80 and some metals with their bulk work functions f (3.66 eV for Mg, 81 4.24 eV for Al(111), 82 5.31 eV for Au(111), 83 5.7 eV for Pt (111), 84 electrodes instead of a single molecule, then polarization energies must be discussed: putting charges on any one molecule will cost somewhat less energy, because partial charges will be induced in the neighboring molecules of the monolayer.…”

Section: Donors and Acceptors; Homos And Lumosmentioning

confidence: 99%

Unimolecular electronics

2008

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“…(1) STS showed that the currents across alkanethiols and aromatic thiols bonded to a Au (111) surface are larger when the molecules are aromatic chains than if they are aliphatic. 21 This result was not surprising, 7 but it has now been obtained by direct measurement.…”

Section: Introductionmentioning

confidence: 99%

Unimolecular Electrical Rectifiers

2003

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research with H. M. McConnell) and post-docs at Stanford (research with P. G. Simpson and M. Boudart), Metzger taught Italian at Stanford (1970− 1971) and chemistry at the University of Mississippi (1971−1986) and the University of Alabama (1986 to present), where he is Professor of Chemistry and former Tricampus Director of the Materials Science Ph.D. Program. Metzger has published 188 papers, edited three books, obtained one patent, graduated 12 Ph.D.'s and 1 M.S., directed the research of 15 undergraduates, and gave talks or spent sabbatical or other leaves in 22 countries. In 1984, he became the first Coulter Professor of Chemistry at the University of Mississippi. In 1998, he received the Blackmon-Moody award of the University of Alabama for exceptional research.

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Photoelectric Emission from Donor-Acceptor Solids and Donor Molecules

Cited by 41 publications

References 27 publications

Modulation of Intersystem Crossing by Chemical Composition and Solvent Effects: Benzophenone, Anthrone and Fluorenone

Modulation of Intersystem Crossing by Chemical Composition and Solvent Effects: Benzophenone, Anthrone and Fluorenone

Unimolecular electronics

Unimolecular Electrical Rectifiers

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