Spin-dependent charge recombination along para-phenylene molecular wires

We have used an efficient new quantum mechanical method for radical pair recombination reactions to study the spin-dependent charge recombination along PTZ$^{\bullet+}$--Ph$_n$--PDI$^{\bullet-}$ molecular wires. By comparing our results to the experimental data of E. Weiss {\em et al.} [J. Am. Chem. Soc. {\bf 126}, 5577 (2004)], we are able to extract the spin-dependent (singlet and triplet) charge recombination rate constants for wires with $n=2-5$. These spin-dependent rate constants have not been extracted previously from the experimental data because they require fitting its magnetic field-dependence to the results of quantum spin dynamics simulations. We find that the triplet recombination rate constant decreases exponentially with the length of the wire, consistent with the superexchange mechanism of charge recombination. However, the singlet recombination rate constant is nearly independent of the length of the wire, suggesting that the singlet pathway is dominated by an incoherent hopping mechanism. A simple qualitative explanation for the different behaviours of the two spin-selective charge recombination pathways is provided in terms of Marcus theory. We also find evidence for a magnetic field-independent background contribution to the triplet yield of the charge recombination reaction, and suggest several possible explanations for it. Since none of these explanations is especially compelling given the available experimental evidence, and since the result appears to apply more generally to other molecular wires, we hope that this aspect of our study will stimulate further experimental work.Comment: 12 pages, 10 figure

Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene (CPF) triad containing considerably more nuclear spins which has recently been used to establish a 'proof of principle' for the operation of a chemical compass [K. Maeda et al., Nature 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C+PF- radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical

Further developments in the local-orbital density-functional-theory tight-binding method

Journal ArticleQuantum-mechanical methods have become increasingly reliable as a complementary tool to experimental research. A variety of methods exist ranging in complexity from semiempirical methods to density-functional-theory (DFT) methods [using either the local-density approximation (LDA) or the generalized-gradient approximation (GGA)] to methods for highly correlated systems (such as multiconfiguration self-consistent field or coupled clusters). Depending on the approximation used, such methods have been effectively applied to a variety of materials and systems

Oscillator strengths and line widths of dipole-allowed transitions in ¹⁴N₂ between 89.7 and 93.5 nm

Line oscillator strengths in the 20 electric dipole-allowed bands of ¹⁴N₂ in the 89.7–93.5nm (111480–106950cm⁻¹) region are reported from photoabsorptionmeasurements at an instrumental resolution of ∼6mÅ (0.7cm⁻¹) full width at half maximum. The absorptionspectrum comprises transitions to vibrational levels of the 3pσᵤc′₄¹Σᵤ⁺, 3pπᵤc³Πᵤ, and 3sσgo₃¹ΠᵤRydberg states and of the b′¹Σᵤ⁺ and b¹Πᵤ valence states. The J dependences of band f values derived from the experimental line f values are reported as polynomials in J′(J′+1) and are extrapolated to J′=0 in order to facilitate comparisons with results of coupled Schrödinger-equation calculations. Most bands in this study are characterized by a strong J dependence of the band f values and display anomalous P-, Q-, and R-branch intensity patterns. Predissociation line widths, which are reported for 11 bands, also exhibit strong J dependences. The f value and line width patterns can inform current efforts to develop comprehensive spectroscopic models that incorporate rotational effects and predissociation mechanisms, and they are critical for the construction of realistic atmospheric radiative-transfer models.This work was supported in part by NASA Grant No. NNG05GA03G to Wellesley College and Australian Research Council Discovery Program Grant No. DP0558962

Sulphur-isotope compositions of pig tissues from a controlled feeding study

Sulphur-isotope determinations are becoming increasingly useful for palaeodietary reconstruction, but knowledge of isotopic discrimination between diet and various tissues remains inadequate. In this study, we explore the sensitivity of δ34Stissue values to changes in δ34Sdiet values, sulphur isotopic discrimination between diet and consumer, and the potential impact of terrestrial vs. marine protein consumption on these discrimination offsets. We present new δ34S values of bone collagen, muscle, liver, hair, milk and faeces from ten mature sows, ten piglets and fifteen adolescent pigs from a controlled feeding study. The δ34Stissue values were found to co-vary with the δ34Sdiet values, the δ34Stissue – δ34Sdiet isotopic offsets (Δ34Stissue-diet) are small but consistent, and dietary protein source does not systematically alter the Δ34Stissue-diet isotopic discrimination. The outcomes of this study are of particular relevance to questions that are difficult to resolve using carbon and nitrogen stable isotopes alone, and will also be useful in regions where terrestrial, freshwater, and marine resources could have all potentially contributed to human diet

Measurement of the thermal diffusivity of building materials

Paper presented at the 6th International Conference on Heat Transfer, Fluid Mechanics and Thermodynamics, South Africa, 30 June - 2 July, 2008.An apparatus was developed to measure the thermal diffusivity of solids with particular emphasis on building materials which do not necessarily have smooth surfaces. Time dependent temperature variations, which may be general, on the cold and hot surfaces of a specimen are used as boundary conditions for a numerical solution of the governing heat flow equation. A least average absolute temperature difference between measured and calculated mid-point temperatures is used to obtain the thermal diffusivity. The apparatus provides a base for the development of improved methods of measuring the thermal properties of materials.vk201

Prayer and psychological health: a study among sixth-form pupils attending Catholic and Protestant schools in Northern Ireland

Eysenck's dimensional model of personality includes two indicators of psychological health, defined as neuroticism and psychoticism. In order to examine the association between psychological health and prayer, two samples of sixth-form pupils in Northern Ireland (16- to 18-year-olds) attending Catholic (N = 1246) and Protestant (N = 1060) schools completed the abbreviated Revised Eysenck Personality Questionnaire alongside a simple measure of prayer frequency. The data demonstrated a positive association between prayer frequency and better levels of psychological health as assessed by Eysenck's notion of psychoticism. Among pupils attending both Catholic and Protestant schools, higher levels of prayer were associated with lower psychoticism scores. Among pupils attending Catholic schools, however, higher levels of prayer were also associated with higher neuroticism scores

A regulated high negative voltage generator for single-photon avalanche photodiodes

In this work, a regulated high negative voltage generator for biasing single-photon avalanche photodiodes (SPAD) was developed. The circuit provides up to -70 V from a positive voltage source. This circuit allows users to control the negative output voltage using a positive voltage rail, thus eliminating the requirement of a negative voltage for the negative voltage control. This approach simplifies the setting of the output and facilitates integration in miniaturized photon counting systems. The testing on a fabricated PCB of this circuit show that the output voltage can be accurately controlled up to -70 V with ripples of less than 80 mV. A SPAD based experimental setup was also built and the experimental results show that the circuit is able to maintain a stable bias voltage for a planar SPAD at both low and high counting rates

Tuning out vibrational levels in molecular electron energy-loss spectra

The phenomenon whereby features associated with certain vibrational levels in molecular states of mixed electronic character disappear under specific scattering conditions in electron energy-loss spectra is investigated. In particular, using a combination of experimental measurements and coupled-channel calculations, anomalous vibrational intensities in the mixed valence-Rydberg 1Π u←X1Σg+ transition of N 2 are explained. A single parameter, i.e., the ratio of the generalized electronic transition moments to the diabatic valence and Rydberg components of the mixed states, dependent on the experimental scattering conditions, is found to be essentially capable of describing all observed relative vibrational intensities, including the near disappearance of the b1Π u(v=5) feature for momentum-transfer-squared values K2 ≈ 0.3 a.u. This result highlights the interesting possibility of experimental control of molecular quantum-interference effects in electron energy-loss spectra, something that is not possible in optical spectra