Systematic Improvement of Empirical Energy Functions in the Era of Machine Learning

The impact of targeted replacement of individual terms in empirical force fields is quantitatively assessed for pure water, dichloromethane (DCM), and solvated K$^+$ and Cl$^-$ ions. For the electrostatics, point charges (PCs) and machine learning (ML)based minimally distributed charges (MDCM) fitted to the molecular electrostatic potential are evaluated together with electrostatics based on the Coulomb integral. The impact of explicitly including second-order terms is investigated by adding a fragment molecular orbital (FMO)-derived polarization energy to an existing force field, in this case CHARMM. It is demonstrated that anisotropic electrostatics reduce the RMSE for water (by 1.6 kcal/mol), DCM (by 0.8 kcal/mol) and for solvated Cl$^-$ clusters (by 0.4 kcal/mol). An additional polarization term can be neglected for DCM but notably improves errors in pure water (by 1.1 kcal/mol) and in Cl$^-$ clusters (by 0.4 kcal/mol) and is key to describing solvated K$^+$, reducing the RMSE by 2.3 kcal/mol. A 12-6 Lennard-Jones functional form is found to perform satisfactorily with PC and MDCM electrostatics, but is not appropriate for descriptions that account for the electrostatic penetration energy. The importance of many-body contributions is assessed by comparing a strictly 2-body approach with self-consistent reference data. DCM can be approximated well with a 2-body potential while water and solvated K$^+$ and Cl$^-$ ions require explicit many-body corrections. The present work systematically quantifies which terms improve the performance of an existing force field and what reference data to use for parametrizing these terms in a tractable fashion for ML fitting of pure and heterogeneous systems

Forensic image analysis – CCTV distortion and artefacts

© 2018 Elsevier B.V. As a result of the worldwide deployment of surveillance cameras, authorities have gained a powerful tool that captures footage of activities of people in public areas. Surveillance cameras allow continuous monitoring of the area and allow footage to be obtained for later use, if a criminal or other act of interest occurs. Following this, a forensic practitioner, or expert witness can be required to analyse the footage of the Person of Interest. The examination ultimately aims at evaluating the strength of evidence at source and activity levels. In this paper, both source and activity levels are inferred from the trace, obtained in the form of CCTV footage. The source level alludes to features observed within the anatomy and gait of an individual, whilst the activity level relates to activity undertaken by the individual within the footage. The strength of evidence depends on the value of the information recorded, where the activity level is robust, yet source level requires further development. It is therefore suggested that the camera and the associated distortions should be assessed first and foremost and, where possible, quantified, to determine the level of each type of distortion present within the footage. A review of the ‘forensic image analysis’ review is presented here. It will outline the image distortion types and detail the limitations of differing surveillance camera systems. The aim is to highlight various types of distortion present particularly from surveillance footage, as well as address gaps in current literature in relation to assessment of CCTV distortions in tandem with gait analysis. Future work will consider the anatomical assessment from surveillance footage

The Phantom Urine: An Unexpected Finding during a Routine Cesarean Section.

We present here an atypical finding during an elective repeat cesarean section. Despite urine flow through an indwelling bladder catheter, bladder remains distended during the whole procedure. Unexpected anatomical variations and malformations can make routine surgery challenging. Urinary tract anomalies should be suspected in cases of unexpected difficult bladder catheterization

Forensic gait analysis — Morphometric assessment from surveillance footage

© 2019 Elsevier B.V. Following the technological rise of surveillance cameras and their subsequent proliferation in public places, the use of information gathered by such means for investigative and evaluative purposes sparked a large interest in the forensic community and within policing scenarios. In particular, it is suggested that analysis of the body, especially the assessment of gait characteristics, can provide useful information to aid the investigation. This paper discusses the influences upon gait to mitigate some of the limitations of surveillance footage, including those due to the varying anatomical differences between individuals. Furthermore, the differences between various techniques applied to assess gait are discussed, including biometric gait recognition, forensic gait analysis, tracking technology, and marker technology. This review article discusses the limitations of the current methods for assessment of gait; exposing gaps within the literature in regard to various influences impacting upon the gait cycle. Furthermore, it suggests a ‘morphometric’ technique to enhance the available procedures to potentially facilitate the development of standardised protocols with supporting statistics and database. This in turn will provide meaningful information to forensic investigation, intelligence-gathering processes, and potentially as an additional method of forensic evaluation of evidence

Losing your virginity safely? A Swiss national survey.

Good practice and knowledge in terms of contraception at first sexual intercourse may lead adolescents to a safer sexual life. To date, research studies have mostly focused on women when investigating contraception use or on condom use only when addressing both genders. The present study adds to the current knowledge by offering a more in-depth view of contraception use at first intercourse among youths. This is achieved through a large selection of variables, the fact that we address both males and females and that we have considered a wide range of contraceptive means. To determine the rate of contraception use at first intercourse by youth in Switzerland and its association with social and personal characteristics. Data were obtained from a self-administrated national survey on sexual behaviour among young adults (mean age 26 years). Participants (n = 4036) were divided into three groups based on the means of contraception used at first intercourse: condom, with or without contraceptive (86.4%), contraceptive only (8.3%) and non-use (5.3%). Only 5.3% did not use any contraception. Compared with the condom group, individuals in the non-use group were more likely to report a lower family socioeconomic status, to be foreign born, to have foreign-born parents, to have a non-intact family and to live in a Catholic canton. They were also more likely to have had their first intercourse in the context of a casual relationship, to have been intoxicated at the time and more likely to regret it. Participants in the contraceptive group reported a higher family socioeconomic status, had intact families, did not live in Catholic cantons, were older and in a steady relationship at first intercourse. Contraception is generally used at first intercourse in Switzerland. Improvements can still be made concerning contraception use in the most vulnerable social strata such as low income families or foreign status

Uncertainty Quantification for Predictions of Atomistic Neural Networks

The value of uncertainty quantification on predictions for trained neural networks (NNs) on quantum chemical reference data is quantitatively explored. For this, the architecture of the PhysNet NN was suitably modified and the resulting model (PhysNet-DER) was evaluated with different metrics to quantify its calibration, the quality of its predictions, and whether prediction error and the predicted uncertainty can be correlated. Training on the QM9 database and evaluating data in the test set within and outside the distribution indicate that error and uncertainty are not linearly related. However, the observed variance provides insight into the quality of the data used for training. Additionally, the influence of the chemical space covered by the training data set was studied by using a biased database. The results clarify that noise and redundancy complicate property prediction for molecules even in cases for which changes – such as double bond migration in two otherwise identical molecules – are small. The model was also applied to a real database of tautomerization reactions. Analysis of the distance between members in feature space in combination with other parameters shows that redundant information in the training dataset can lead to large variances and small errors whereas the presence of similar but unspecific information returns large errors but small variances. This was, e.g., observed for nitro-containing aliphatic chains for which predictions were difficult although the training set contained several examples for nitro groups bound to aromatic molecules. The finding underlines the importance of the composition of the training data and provides chemical insight into how this affects the prediction capabilities of a ML model. Finally, the presented method can be used for information-based improvement of chemical databases for target applications through active learning optimization

Assignment of the evidential value of a fingermark general pattern using a Bayesian network

Abstract: When visible on a fingermark, the general pattern maintains its importance in the fingerprint examination procedure, since the difference between the general pattern of a fingermark and a fingerprint is sufficient for exclusion. In the current work, the importance of the general pattern is extended by evaluating the strength of evidence of a match given corresponding general pattern. In current practice (due to the lack of statistical support for the general pattern evidence) the fingerprint examiners assign personal probabilities to the general pattern evidence based on their knowledge and experience, while in this work the probabilities are calculated using a Bayesian Network which is fed by empirical data. 1

Molecular-Level Understanding of the Ro-vibrational Spectra of N2_2O in Gaseous, Supercritical and Liquid SF6_6 and Xe

The transition between the gas-, supercritical-, and liquid-phase behaviour is a fascinating topic which still lacks molecular-level understanding. Recent ultrafast two-dimensional infrared spectroscopy experiments suggested that the vibrational spectroscopy of N$_2$O embedded in xenon and SF$_6$ as solvents provides an avenue to characterize the transitions between different phases as the concentration (or density) of the solvent increases. The present work demonstrates that classical molecular dynamics simulations together with accurate interaction potentials allows to (semi-)quantitatively describe the transition in rotational vibrational infrared spectra from the P-/R-branch lineshape for the stretch vibrations of N$_2$O at low solvent densities to the Q-branch-like lineshapes at high densities. The results are interpreted within the classical theory of rigid-body rotation in more/less constraining environments at high/low solvent densities or based on phenomenological models for the orientational relaxation of rotational motion. It is concluded that classical MD simulations provide a powerful approach to characterize and interpret the ultrafast motion of solutes in low to high density solvents at a molecular level

Long-range versus short-range effects in cold molecular ion-neutral collisions

The investigation of cold interactions between ions and neutrals has recently emerged as a new scientific frontier at the interface of physics and chemistry. Here, we report a study of charge-transfer (CT) collisions of Rb atoms with N[Formula: see text] and O[Formula: see text] ions in the mK regime using a dynamic ion-neutral hybrid trapping experiment. We observe markedly different CT kinetics and dynamics for the different systems and reaction channels studied. While the kinetics in some channels are consistent with classical capture theory, others show distinct non-universal dynamics. The experimental results are interpreted with the help of classical-capture, quasiclassical-trajectory and quantum-scattering calculations using ab-initio potentials for the highly excited molecular states involved. The theoretical analysis reveals an intricate interplay between short- and long-range effects in the different reaction channels which ultimately determines the CT dynamics and rates. Our results illustrate salient mechanisms that determine the efficiency of cold molecular CT reactions