Searcharxiv⌕ Search
Home/Archive/arXiv

arXiv · 1901.06320

Using Structurally Well-Defined Norbornyl-Bridged Acene Dimers to Map a Mechanistic Landscape for Correlated Triplet Formation in Singlet Fission

Alexander T. Gilligan·Ethan G. Miller·Tarek Sammakia·Niels H. Damrauer
View original source ↗Read source document ↗Export metadata ↓

Abstract

Structurally well-defined TIPS-acetylene substituted tetracene (TIPS BT1') and pentacene (TIPS BP1') dimers utilizing a [2.2.1] bicyclic norbornyl bridge have been studied -primarily using time-resolved spectroscopic methods - to uncover mechanistic details about primary steps in singlet fission leading to formation of the biexcitonic 1TT state as well as decay pathways to the ground state. For TIPS BP1' in room temperature toluene, 1TT formation is rapid and complete, occurring in 4.4 ps. Decay to the ground state in 100 ns is the primary loss pathway for 1TT in this system. For TIPS BT1', the 1TT is also observed to form rapidly (with a time constant of 5 ps) but in this case it occurs in concert with establishment of an excited state equilibrium (K~1) with the singlet exciton state S1 at an energy of 2.3 eV above the ground state. The equilibrated states survive for 36 ns and are lost to ground state through both radiative and non-radiative pathways via the S1 and non-radiative pathways via the 1TT. The rapidity of 1TT formation in TIPS BT1' is at first glance surprising. However, our analysis suggests that the few-parameter rate constant expression of Marcus theory explains both individual and comparative findings in the set of systems, thus establishing benchmarks for diabatic coupling and reorganization energy needed for efficient 1TT formation. Finally, a comparison of TIPS BT1' with previous results obtained for a close constitutional isomer (TIPS-BT1) differing in the placement of TIPS-acetylene side groups suggests that the magnitude of exchange interaction in the correlated triplet manifold plays a critical role dictating 1TT yield in the tetracenic systems.

Explore related subjects

physics.chem-phcond-mat.mtrl-sci

Keep this discovery

BibTeXRIS

Alexander T. Gilligan, Ethan G. Miller, Tarek Sammakia, Niels H. Damrauer. 2019-01-18. Using Structurally Well-Defined Norbornyl-Bridged Acene Dimers to Map a Mechanistic Landscape for Correlated Triplet Formation in Singlet Fission. https://arxiv.org/abs/1901.06320

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

arXiv2026

Breaking Water at Graphene Defects

Water dissociation at solid surfaces underpins processes ranging from corrosion and catalysis to electrochemistry and photovoltaics. Defects often serve as reactive sites for dissociation, yet how solvation influences water dissociation at such sites remains poorly understood. Here, we use state-of-the-art machine-learned interatomic potentials to explore water dissociation at defective graphene-water interfaces. We show that solvation qualitatively changes the reaction mechanism at a graphene single vacancy (SV), opening pathways that are absent for an isolated water molecule. Whereas the gas-phase process proceeds via a single concerted channel, the solvated SV splits water through two competing pathways: a basic route forming SV-H and OH-(aq), and an acidic route forming SV-OH and H3O+(aq). These lower-barrier pathways produce distinct chemisorbed intermediates that enhance graphene-water adsorption. Accordingly, even a simple carbon vacancy gives rise to unexpectedly rich interfacial chemistry, coupling surface chemistry to interfacial charge and wettability, with implications for carbon functionalization and nanofluidic transport.

physics.chem-ph↗
arXiv2026

Comprehensive Study of L-Menthol and Octanoic Acid as a Hydrophobic Eutectic Solvent

Hydrophobic eutectic solvents (HES) based on natural compounds represent promising green alternatives to conventional solvents. In this work, we investigate the physicochemical, structural, and dynamical properties of an ES formed by L-menthol and octanoic acid using a combined experimental and molecular dynamics simulation approach. Five compositions with molar ratios from 1:3 to 3:1 were studied with molecular dynamics simulation in the temperature range 15 degrees C to 35 degrees C. Experimental measurements of density and viscosity in the temperature range from 5 degrees C to 35 degrees C were complemented with results obtained from MD simulations employing the OPLS force field. Structural analyses based on radial distribution functions and Kirkwood-Buff integrals reveal that the dominant interactions in the mixture are hydrogen bonds between L-menthol and octanoic acid molecules. Dynamic properties, including self-diffusion coefficients and hydrogen-bond lifetimes, indicate that intermolecular hydrogen bonds between the two components are stronger and longer-lived than bonds between identical species. These findings provide molecular-level insight into the structure and transport properties of menthol-based ESs relevant for green solvent applications.

physics.chem-ph↗
arXiv2026

More is not always better: Dissociative photoionization limits the EUV absorbing photacid generator pentafluorophenyl triflate in photolithography

Pentafluorophenyl triflate has been explored as a highly absorbing neutral photoacid generator (PAG) candidate for next generation chemically amplified resists used in extreme ultraviolet (EUV) lithography. Although increased fluorination enhances EUV absorption, this study demonstrates that such an approach does not necessarily improve photoacid generation efficiency. Using photoelectron-photoion coincidence (PEPICO) spectroscopy at the 92 eV photon energy of the EUV scanners in combination with quantum chemical calculations, the dissociative photoionization of pentafluorophenyl triflate was systematically investigated. The photoionization mass spectrum reveals extensive fragmentation, with the parent ion contributing only 3.1 % of the total signal and CF$_3^+$ representing the dominant product ion. Computed appearance energies align well with experimental trends and support a sequential fragmentation pathway involving loss of SO$_2$, CF$_3$, and CO. Crucially, none of the major dissociation channels yield precursors capable of forming triflic acid, the strong photoacid required for efficient deprotection reactions in chemically amplified resists. Combined with previous dissociative electron attachment studies indicating similarly unfavorable fragmentation, the results demonstrate that despite its high EUV absorption cross section, pentafluorophenyl triflate is unsuitable as a PAG for EUV lithography. The findings highlight the importance of understanding fundamental photoionization and electron interaction mechanisms to guide the rational design of next generation high performance EUV photoresists.

physics.chem-ph↗