arXiv subjects

Samuel L. Smith

Publications and source records attributed to Samuel L. Smith.

22 records · Page 2Linked to original sources

arXiv2017

Energy Efficient Dissociation of Excitons to Free Charges

In photovoltaics (PVs) and artificial photosynthetic systems based on excitons, the question of how energy must be lost in overcoming the Coulomb barrier, converting excitons to free charges, is fundamental, as it determines the achievable open-circuit voltage or over-potential1-3. Here, using transient and steady-state optical spectroscopy we study a model system, pentacene/C60, where pentacene triplet excitons are dissociated to form charge transfer states, which we show to be degenerate in energy with the triplet excitons. We directly track these charge transfer states undergoing efficient long-range separation to free charges within 50 ps, despite a significant Coulomb barrier that we measure to be 220 meV. We model this endothermic charge separation to be driven by entropic gain. Our results demonstrate that endothermic charge separation can proceed rapidly with near unity efficiency, overcoming Coulomb barriers greater than 200meV via a gain in entropy, thus minimising loss of open-circuit voltage or over-potential. In the pentacene/C60 system this leads here to an effective VOC loss of only 400meV with respect to the energy of the triplet exciton. This suggests that excitonic photoconversion systems have no fundamental disadvantage compared to systems which generate free changes directly upon photoexcitation.

cond-mat.mes-hall↗

arXiv2017

Offline bilingual word vectors, orthogonal transformations and the inverted softmax

Usually bilingual word vectors are trained "online". Mikolov et al. showed they can also be found "offline", whereby two pre-trained embeddings are aligned with a linear transformation, using dictionaries compiled from expert knowledge. In this work, we prove that the linear transformation between two spaces should be orthogonal. This transformation can be obtained using the singular value decomposition. We introduce a novel "inverted softmax" for identifying translation pairs, with which we improve the precision @1 of Mikolov's original mapping from 34% to 43%, when translating a test set composed of both common and rare English words into Italian. Orthogonal transformations are more robust to noise, enabling us to learn the transformation without expert bilingual signal by constructing a "pseudo-dictionary" from the identical character strings which appear in both languages, achieving 40% precision on the same test set. Finally, we extend our method to retrieve the true translations of English sentences from a corpus of 200k Italian sentences with a precision @1 of 68%.

cs.CL↗

arXiv2015

Disorder in the spectral function of a qubit ensemble

The impact of disorder in the vibrational bath of an ensemble of open quantum systems is explored, arising either from variation in the overall coupling strength or from uncertainty in the shape of the environment spectral function. Such disorder leads to an additional source of decoherence of subsystem ensembles, due to variation in the reorganization energy. Additionally, vibrational disorder induces a shift in the oscillation frequency of the coherence between ground and excited states. This shift is temperature dependent, and in the high temperature limit $δω\propto T$. This latter finding could be of particular relevance to biological systems exhibiting long lived coherences in highly disordered environments, where temperature-dependent quantum beats have been observed.

quant-ph↗

arXiv2014

Phonon-Assisted Ultrafast Charge Separation in a Realistic PCBM Aggregate

Organic solar cells must separate strongly bound electron-hole pairs into free charges. This is achieved at interfaces between electron donor and acceptor organic semiconductors. The most popular electron acceptor is the fullerene derivative PCBM. Electron-hole separation has been observed on femtosecond timescales, which is incompatible with conventional Marcus theories of organic transport. In this work we show that ultrafast charge transport in PCBM arises from its broad range of electronic eigenstates, provided by the presence of three closely spaced delocalised bands near the LUMO level. Vibrational fluctuations enable rapid transitions between these bands, which drives an electron transport of $\sim$3 nm within 100 fs. All this is demonstrated within a realistic tight binding Hamiltonian containing transfer integrals no larger than 8 meV.

cond-mat.mtrl-sci↗