Faraday Community poster symposium

Faraday Community poster symposium 10 November 2023, London, UK

10 November 2023, London, UK Faraday Community poster symposium

Book of abstracts

Registered charity number: 207890

Welcome

Dear Colleagues, Welcome to the first Faraday Community poster symposium, designed to celebrate the breadth and strength of research in physical chemistry by researchers in the early stages of their careers. We hope you enjoy the day and take advantage of the opportunities to network and learn about the latest physical chemistry research. There are prizes on offer today for the best posters as selected by our panel of judges. Participants today will also be able to vote for their favourite poster, which will win a prize of a gift voucher for an RSC book. We are extremely grateful to the RSC journals PCCP and Faraday Discussions for sponsoring the prizes today. We are delighted to have a range of delegates here today from across the physical chemistry community. This meeting would not be possible without the enthusiastic support of all of the delegates, the organising committee, the prize judges and the careers panellists who have given up their time to join us today, and I wish to offer them my thanks. It only remains for me to welcome you once again, to thank you all for travelling here, and to wish you an enjoyable and stimulating time at the symposium. Best wishes,

Dwayne Heard President, Faraday Community for Physical Chemistry

Physical Chemistry at the Royal Society of Chemistry The Faraday Community for Physical Chemistry is one of seven Subject Communities of the Royal Society of Chemistry which its members can join. The Faraday Community for Physical Chemistry is comprised of nearly 6 000 members from all over the world, from academia and industry and represent all career stages. The community is led by a council elected by the membership and appointed by the council and related interest groups to represent the entire physical chemistry community. Our aims are to: • To advise on and support scientific developments both in research and training in the general field of physical chemistry . • To support the next generation of scientists in the important field of physical chemistry in its broadest context . • To act as an advocate for the field of physical chemistry to the scientific community, and society as a whole. • To promote excellence and sustainability in the field of physical chemistry. • To promote inclusion and diversity in its broadest possible sense across the physical chemistry community. We organise and / or support a range of activities, such as the Faraday Discussions conference series , the Faraday Joint Interest Group Conference, the Faraday Community Poster Symposium, and small scientific meetings. We support community-led events, such as the Recent Appointees in Physical Chemistry meeting. We advocate and provide expertise for physical chemistry. We recognise excellence within the community through our prizes programme and support our community by supporting the RSC grants schemes. Find out more: https://rsc.li/ faraday-community Contact us: science@rsc.org

Scientific Committee

Poster Judges

Prof. Helen Fielding Prof. Andrew Mount Dr Marco Sacchi Prof. Alice Thorneywork Dr Cristina Trujillo Dr Simon Port

P rof. Dwayne Heard (Chair) University of Leeds , UK Prof. Elena Besley University of Nottingham, UK Prof. Brianna Heazlewood University of Liverpool , UK Dr Marco Sacchi University of Surrey , UK Dr Cristina Trujillo University of Manchester, UK

Careers Panellists

Dr Paul Brewer Dr Lauren Hatcher Prof. Claire Vallance

Sponsors

Poster presentations

CO 2 capture via oxalate formation in metal-decorated graphene Inioluwa Afolabi University of Cambridge, UK Zwitterions modulate interfacial interactions across electrolyte solutions Kieran Agg University of Oxford, UK Feature identification in molybdenum carbides: graph neural networks vs. human empirical search – who’s the winner? Eduardo Aguilar Bejarano University of Nottingham, UK Implementing a data driven pipeline for supramolecular drug design - challenges and FAIR practices Thomas Allam University of Southampton, UK Operando x-ray absorption & inelastic neutron scattering studies of novel thermoelectric metal-organic-frameworks Rob Clarke University of Southampton, UK Simulating nonadiabatic dynamics using the Meyer-Miller-Stock-Thoss Hamiltonian: a comparison of algorithms Lauren Cook University College London, UK Computational treatment of lanthanide dopants in oxides by DFT with Hubbard corrections Dan Criveanu University of Nottingham, UK The conformational preference of 2-ethylthiazole and its weakly bound complexes with water revealed by microwave spectroscopy Charlotte Cummings Newcastle University, UK

P01

P02

P03

P04

P0 6

P07

P08

P09

Using chemical kinetics models to unravel the origin of excess carbon and lack of nitrogen in planet-forming environments Javiera Diaz Berrios University of Leeds, UK Spatial and temporal detection of ions ejected from Coulomb crystals using Timepix3 Jake Diprose University of Liverpool, UK Versatile ion current rectifying nanopipette sensors for biological (pathogenic DNA) and non-biological (pesticide) molecule detection Pallavi Dutta University College Dublin, Ireland Exploring the complex chemistry of biomass burning emissions Rhianna Evans University of York, UK Probing anomalous underscreening with a protic ionic liquid between charged interfaces Y.K. Catherine Fung University of Oxford, UK Application of laser flash photolysis combined with time-resolved broadband UV absorption spectroscopy to measure the total OH radical reactivity Midhun George University of Leeds, UK Unravelling the photochemical pathways for aqueous p-nitrophenol excited by 320 nm ultraviolet radiation Deborin Ghosh University of Bristol, UK Theoretical design rules for tailoring organic chromophore spectra for optoelectronic applications. James Green UCL, UK

P10

P11

P12

P13

P14

P15

P16

P1 8

P19

A world of probabilities: an sMD/MSM approach for rational design of allosteric modulators Adele Hardie University of Edinburgh, UK Predicting NaCl morphology: are kinetic monte carlo methods enough? John Hayton University of Cambridge, UK Analysing replica exchange simulations of conotoxin peptides Charlie Holdship University of Southampton, UK Simulating excited states in metal organic frameworks: from light-absorption to photochemical CO 2 reduction Michael Ingham University College London (UCL), UK Ultrashort, deep-ultraviolet pulses by resonant dispersive wave emission from hollow capillary fibres for time-resolved photoelectron imaging Seb Jackson Heriot-Watt University, UK Improving sulfur chemistry over the ocean: developing and evaluating a DMS mechanism Lorrie Jacob University of Cambridge, UK Temperature dependence time-resolved luminescence spectroscopy in synthetic NV0 centers Ffion James Cardiff University, UK Surface science investigations into the interstellar molecule propylene oxide Kerry Jones University of Sussex, UK Investigating the spatial distribution of inductively coupled plasmas using spectroscopy and plasma modelling simulations Charlie Kniebe-Evans Department of Physical & Theoretical Chemistry, University of Oxford, UK

P20

P21

P22

P23

P24

P25

P26

P27

P28

Kinetics of the reaction of the criegee intermediate CH 2 OO with water Rachel Lade University of Leeds, UK Optical and morphological properties of light absorbing internally mixed aerosol particles Gwen Lawson University of Bristol, UK Organosulfates in the polluted atmosphere: compositions, origins and formation mechanisms Ping Liu Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, China Laboratory studies of reactive intermediates in atmospheric chemistry Kate Livesey University of Leeds, UK Electrosynthesis of cobalt imidazolate framework using bio solvents as a solvent medium to produce high crystalline MOFs tested for supercapacitor application Vijayakumar Manavalan Aston University, UK Detailed structural information of conjugated polymers revealed by high resolution scanning tunnelling microscopy Paola Mantegazza University of Birmingham, UK

P29

P30

P31

P32

P33

P34

Cold plasma recycling of plastics Mariano Marco Tobias Heriot-Watt University, UK

P35

Multidentate halogen-bond based catalysis: a computational study Nika Melnyk Trinity College Dublin, Ireland

P36

Roles of interfacial water in carbon mineralisation Shurui Miao University of Oxford, UK

P37

Validating emission fluxes calculation of anthropogenic greenhouse gas emissions Irene Monreal Campos FAAM Airbone Laboratory, UK

Cryogenic ion trap to study state- and velocity-selected radical-ion reactions Rahul Kumar Pandey University of Liverpool, UK IR-PD spectroscopy of the astrochemically relevant HCCS+ and [C 2 H 2 S]+ ions Vincent Richardson University of Liverpool, UK The site-specific kinetics of methyl formate, CH 2 OC(O)H Niamh Robertson University of Leeds, UK Radical collisions with liquid surfaces: from pure sources to scattering mechanisms Maksymilian Roman University of Liverpool, UK Significant missing OH reactivity measured at a remote tropical marine site Samuel Seldon University of Leeds, UK The microphysics of surrogates of exhaled aerosols from the upper respiratory tract Jianghan Tian University of Bristol, UK State- and velocity-selected radicals for cold, controlled reaction studies Lok Yiu Wu University of Liverpool and University of Oxford, UK Photoresist-assisted semi-dry transfer of graphene onto functional substrates Jincan Zhang University of Cambridge, UK

P39

P4 1

P4 2

P4 4

P4 5

P4 6

P4 7

P4 8

CO 2 capture via oxalate formation in metal-decorated graphene Inioluwa C. Afolabi 1 , Yasmine Alham-dani 2 , Ben Shi 1 , Andrea Zen 3 , Angelos Michealides 1 1 Yusuf Hamied Department of Chemistry, University of Cambridge, UK, 2 Department of Earth Sciences, University College London, UK; 3 Dipartimento di Fisica Ettore Pancini, Università di Napoli Federico II, Italy Carbon capture, utilization and storage (CCUS) is an active research area today because of its importance in mitigating the effects of climate change. For CCUS to thrive, there is a need for high-performing materials that could capture CO 2 sustainably and preferably convert it to a useful chemical feedstock. Graphene as a carbon material possesses excellent properties such as high surface area making it suitable for gas storage applications. However, it has been reported to bind CO 2 too weakly for viable capture [1,2]. Metal decoration has been predicted to strengthen the adsorption energy, but it is unclear if it could foster the conversion of CO 2 to a useful chemical intermediate in graphene-based materials [3]. This work harnessed density functional theory with random structure search to understand the adsorption of CO 2 on metal-decorated graphene. The adsorption of 1-7 CO 2 on 5 metal-decorated graphene systems (Na, K, Ca, Sr and Ti) is considered. Generally, the adsorption strength of the metal atoms for CO 2 increases in the order Ti > Ca > Sr > Na > K and the increased strength seen in Ti, Ca and Sr is due to the formation of oxalate(s). Analysis of the electronic structure in the systems considered reveals that the governing adsorption mechanism involves an ionic charge transfer from the metal adatom to the CO 2 molecules, resulting in bent reactive CO 2 anion, which dimerises to form an oxalate upon the adsorption of 2 CO 2 molecules. It is also found that the maximum number of CO 2 that can be chemisorbed in Ca, Sr and Ti relates to the valence charge on the metal atom; with Ca and Sr having the maximum capacity for 2 CO 2 and Ti, 4 CO 2 in the form of oxalate(s). The oxalate(s) formed in these materials give new insight into their capacity for CO 2 sequestration and their viability for CCUS applications. References 1. Chu, S., & Majumdar, A. (2012). Opportunities and challenges for a sustainable energy future.nature,488(7411), 294-303.C. Wang, Y. Fang, H. Duan, G. Liang, W. Li, D. Chen, and M. Long, “Dft study of co2 adsorption properties on pristine, vacancy and doped graphenes,” Solid State 2. Communications, vol. 337, 10 2021.Y. Lu, Y. Xu, J. Zhang, Q. Zhang, L. Li, and J. Tian, “Adsorption of carbon dioxide gas by modified graphene: A theoretical study,” ChemistrySelect, vol. 7, 2 2022.

P01

Zwitterions modulate interfacial interactions across electrolyte solutions Kieran Agg, Susan Perkin University of Oxford, UK Cellular functionality relies on the ability to maintain structure and function of biological macromolecules such as proteins, key to which is the surrounding chemical environment: the cytosol. Cytosol composition not only dictates the osmotic balance of cells with their surroundings, but also determines the range and nature of inter-protein interactions within the cell 1 . While the role of ionic solutes in destabilising proteins is well known, as illustrated by the Hofmeister series, the role that zwitterionic “osmolytes” play in these interactions is less clear. Here we will present a study of surface force measurements across model cytosol solutions, some of which have been recently reported 2 . These aqueous solutions containing pure zwitterion and salt-zwitterion mixtures reveal that common osmolytes such as trimethyl glycine and proline act to influence the interaction potential between charged mica sheets, including by enhancing the strength and range of electrostatic repulsion, disrupting water structure and forming molecular layers at charged interfaces. This multifaceted nature of zwitterionic osmolytes may be significant in how these molecules impart stability and balance in the cellular environment. References 1. Wennerström, H., Vallina Estrada, E., Danielsson, J., & Oliveberg, M. (2020). Colloidal stability of the living cell. Proc. Natl. Acad. Sci. , 117 (19), 10113–10121. 2. Hallett, J. E., Agg, K. J., & Perkin, S. (2023). Zwitterions fine-tune interactions in electrolyte solutions. Proc. Natl. Acad. Sci. , 120 (8),

P02

Feature identification in molybdenum carbides: graph neural networks vs. human empirical search – who’s the winner? Eduardo Aguilar Bejarano 1,2,3 , Luis Arrieta Araya 4 , Mauricio Gutierrez 5 , Grazziela Figueredo 3 , Ender Özcan 3 , Simon Woodward 1,2 , Ignacio Borge-Durán 6 1 The Glaxo Smith Kline Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, UK, 2 School of Chemistry, University of Nottingham, UK, 3 School of Computer Science, University of Nottingham, UK, 4 School of Chemical Engineering, University of Costa Rica, Costa Rica, 5 School of Chemistry, University of Costa Rica, Costa Rica, 6 School of Chemistry, Bar-Ilan University, Israel Transition metal carbides (TMCs) are materials with a wide range of applications due to their interesting properties. Such properties are correlated to crystalline ordered-disordered phase transitions, that occur when heating or cooling the TMC. Understanding the energetics of this process allows tuning of TMCs properties for a given application. Traditionally, DFT calculations have been used to try to model TMC structures, and phase transitions through understanding the distribution of the carbon (carbide) atoms within the overall metal lattice. Unfortunately, DFT is computationally expensive for solid state TMCs, and for large lattices DFT models are presently untenable. A simple empirical model [1] is presently used as a DFT replacement for MoC 0.5 systems, using three different variables related to the distribution of carbide atoms within the molybdenum lattice. The phase transition predictions of this simple model are now very accurate. Unfortunately, this required months of trial-and-error screening for the (human) investigators to figure out the best features to represent the cell thus allowing energetic predictions. Herein, we evaluate the performance of an automated feature generation approach using a Graph Neural Network ( GNN ) to predict the internal energy of MoC 0.5 . We have collected a total of 1065 molybdenum carbide structures with their corresponding DFT calculated internal energy. The structures were represented as graphs, where the atoms are represented as nodes and atom-to-atom interactions as edges. The nodes were loaded with node features of atom identity (whether it is carbon or molybdenum) and its encoded 3D coordinates. We have applied a 5-k-fold strategy to evaluate the generalisability and robustness of the model. [2] The statistics of our approach for the 5 folds (mean ± std) are: R 2 0.923 ± 0.005 , M AE 0.133 ± 0.003, RMSE 0.172 ± 0.002. When using the empiric model, the metrics obtained for the 1065 structures are: R 2 0.928 ± 0.014 , M AE 0.129 ± 0.007, RMSE 0.165 ± 0.013. A T-test has shown that there is not statistical difference between models, which means that GNNs are able to learn and predict on this system within the same accuracy as a human do, but only taking 10 minutes of training per model. References 1. Ignacio Borge-Durán, Denial Aias, and Ilya Grinberg. Modelling of high-temperature order–disorder phase transitions of non- stoichiometricMo2C and Ti2C from first principles. PhysicalChemistry Chemical Physics, 23(39):22305–22312,2021. 2. Eduardo Aguilar, Luis Arrieta, Mauricio Gutierrez, Grazziela Figueredo, Ender Ozcan, Simon Woodward, Ignacio Borge, manuscript in preparation.

P03

Implementing a data driven pipeline for supramolecular drug design - challenges and FAIR practices

Thomas Allam 2 , Jennifer Hiscock 1 , Prof. Jeremy Frey 2 1 University of Kent, UK, 2 University of Southampton, UK

In academia, a large proportion of data sharing and analysis is conducted using spreadsheets. In this talk, we will discuss the advantages that come with the implementation of FAIR (Findable, Accessible, Interoperable, and Re-usable) databases to structure and share interdisciplinary siloed data from across multiple research groups. We will discuss our experience setting up and using data pipelines in academia and the challenges and benefits of doing so. We have attempted to implement data pipelines to store small and highly varied datasets of supramolecular molecules. In this poster we discuss how we have curated and structured the datasets, our attempt to model the small datasets to try to get insight into the mechanism of action of the compounds and our future plans for the work. References 1. Wilkinson et al. The FAIR Guiding Principles for scientific data management and stewardship. Sci Data 3, 160018 (2016). 10.1038/sdata.2016.18 2. Hiscock, J. R et al, In situ modification of nanostructure configuration through the manipulation of hydrogen bonded amphiphile self-association, 10.1039/C6SM00529B 3. Allen et al, Towards the Prediction of Antimicrobial Efficacy for Hydrogen Bonded, Self‐Associating Amphiphiles, 10.1002/ cmdc.202000533 4. Reller, L. B et al, Antimicrobial susceptibility testing: a review of general principles and contemporary practices, 10.1086/647952 5. Antimicrobial resistance : tackling a crisis for the health and wealth of nations / the Review on Antimicrobial Resistance chaired by Jim O'Neill

P04

Operando x-ray absorption & inelastic neutron scattering studies of novel thermoelectric metal-organic-frameworks Rob Clarke 1 , Dr. Iris Nandhakumar 1 , Dr. Darren Bradshaw 1 , Dr. Luke Keenan 2 , Dr. Svemir Rudic 3 1 School of Chemistry, University of Southampton, UK, 2 Diamond Light Source, Harwell Research and Innovation Campus, Oxfordshire, UK, 3 ISIS Neutron and Muon Source, Didcot, UK Thermoelectrics (TEs) are an important class of materials that can directly convert thermal waste heat into useful electrical energy and have great potential to contribute to the sustainability agenda. Despite such possibilities, barriers exist to their widespread adoption due to the low efficiency of current materials. TE power generation has the potential of becoming a transformative technology for renewable energy generation, provided that the low efficiency of current TE materials can be addressed by developing novel materials. Metal-organic frameworks (MOFs) are a class of solid-state materials which are comprised of a self-assembled lattice structure of positive metal ions or clusters coordinated to negative anionic ‘linkers’.MOFs are attractive candidates for novel TE materials given their relatively low thermal conductivity and tunable electrical conductivity [1]. Although most MOFs tend to be insulators, significant progress has been made over the last five years exploiting both ‘through-bond’ and ‘through-space’ charge transport pathways in these frameworks[2]. Cu 3 (HHTP) 2 (Figure 1.) and Ni 3 (HITP) 2 are semiconductive 2D layered MOFs which demonstrate promising TE capabilities. Their honeycomb framework allows electron transport between the π-π stacking of the organic linker, allowing ‘through-space’ charge transport. [3]We have reported a high electrical conductivity (15.4 S m -1 ) in addition to an impressive Seebeck coefficient(+419.5 µV K -1 ) for these materials. We have also demonstrated how doping Cu 3 (HHTP) 2 thin films by incipient wetness impregnation with molecular iodine significantlyimproves the electrical conductivity and power factor. However, the exact mechanism of doping or what species are responsible for charge transport after doping is still unknown and is yet to be systematically investigated. Preliminary HERFD XANES studies have suggested doping causes a change in oxidation state of the Cu 2+ centre which may contribute to the improve electrical conductivity. Moreover, further studies will be performed on both Cu 3 (HHTP) 2 and Ni 3 (HITP) 2 frameworks, at beamline I20 and Diamond Light Source and Tosca at ISIS, to elucidate the structure-property relationship in these systems.

Figure 1: Structural representation of Cu 3 (HHTP) 2 metal-organic-framework Code: Copper (orange), carbon (grey) and oxygen (red). References 1. S. Ma and H. C. Zhou, Chemical Communications , 2010, (46), 44–53. 2. M. De Lourdes Gonzalez-Juarez, C. Morales, J. I. Flege, E. Flores, M. Martin-Gonzalez, I. Nandhakumar and D. Bradshaw, ACS Appl Mater Interfaces , 2022, (14), 12404–12411. 3. Winkler, C. & Zojer, E. Nanomaterials , 2020, (10), 1–21.

P06

Simulating nonadiabatic dynamics using the meyer-miller-stock- thoss hamiltonian: a comparison of algorithms Lauren E. Cook 1 , Johan E. Runeson 2 , Jeremy O. Richardson 2 , Timothy J. H. Hele 1 1 Department of Chemistry, University College London, UK, 2 Laboratory of Physical Chemistry, ETH Zürich, Switzerland Mixed quantum-classical models are commonly used to simulate nonadiabatic dynamics. Often, these approaches use a mapping to describe the electronic dynamics by time-propagating a set of classical variables, where averaging over many trajectories allows the approximation of thermal equilibrium properties through correlation functions. Many integration algorithms exist to propagate the dynamics, but a through performance comparison appears to be lacking. Here, we compare three time-propagation algorithms for the Meyer-Miller- Stock-Thoss Hamiltonian: the MInt, Split-Liouvillian (SL), and Degenerate Eigenvalue (DE) algorithms. 1–3 We determine that the MInt is the most accurate algorithm based on the symplecticity, energy conservation, computational cost, and accuracy of correlation functions. Despite not being symplectic, the SL algorithm obtains similar results for a lower computational cost and in some cases, better energy conservation. Approximations within the DE algorithm results in inaccurate dynamics, poor energy conservation and a higher computational expense for systems with weak electronic coupling. These results should guide future simulations utilising mapping variable approaches. References

1. M. S. Church, T. J. H. Hele, G. S. Ezra, and N. Ananth, J. Chem. Phys. 148 , 102326 (2018). 2. J. O. Richardson, P. Meyer, M.-O. Pleinert, and M. Thoss, Chem. Phys. 482 , 124 (2017). 3. A. Kelly, R. van Zon, J. Schofield, and R. Kapral, J. Chem. Phys. 136 , 084101 (2012).

P07

Computational treatment of lanthanide dopants in oxides by DFT with Hubbard corrections Dan Criveanu, Katherine Inzani School of Chemistry, University of Nottingham, UK Density functional theory (DFT) is a computationally efficient choice for computing the quantum chemical properties of material systems. However, electron over-delocalization presents a problem in the DFT treatment of lanthanide elements as d - and f -electrons are highly localised. 1 One way to address this is with additive corrections to the DFT energy such as DFT+U 2-4 , in which a Hubbard U parameter is introduced to enforce localisation of a given subshell. This method has been highly successful for transition metals, and recent developments have also shown its applicability in the treatment of lanthanide compounds. 5,6 Here, we investigate the use of these methods for lanthanide dopants in wide band gap oxides. Using cerium-doped yttrium aluminium garnet (YAG:Ce) as a model system, we compare the effect of DFT+U corrections on the electronic structure, and we show the limitations of self-consistent determination of U. 7 Furthermore, we explore methods that address metastability issues introduced by DFT+U, 8-10 which are particularly problematic for f -electron systems. 10 We identify occupation matrix control 8 as the preferred method to address metastability issues in YAG:Ce due to its ability to find the lowest energy electronic state compared to U-ramping. 9 Successful implementation of such low-computational cost corrections would enable further theory-led innovations in lanthanide-doped oxides, with wide-ranging implications from lighting to quantum technologies. References 1. K. Capelle and V. L. Campo, Phys. Rep., 2013, 528, 91–159. 2. V. I. Anisimov et al., Phys. Rev. B, 1991, 44, 943–954. 3. A. I. Liechtenstein et al., Phys. Rev. B, 1995, 52, R5467–R5470. 4. S. L. Dudarev et al., Phys. Rev. B, 1998, 57, 1505–1509. 5. A. Canning et al.,Phys. Rev. B, 2011,83, 125115.

6. A. Blanca Romero et al.,J. Comput. Chem., 2014,35, 1339–1346. 7. M. Cococcioni and S. de Gironcoli, Phys. Rev. B, 2005, 71, 035105. 8. B. Dorado et al., Phys. Rev. B, 2010, 82, 035114. 9. B. Meredig et al., Phys. Rev. B, 2010, 82, 195128. 10. J. P. Allen and G. W. Watson,Phys. Chem. Chem.Phys., 2014,16, 21016–21031.

P08

The conformational preference of 2-ethylthiazole and its weakly bound complexes with water revealed by microwave spectroscopy Charlotte Cummings, Nick Walker Newcastle University, UK Microwave spectroscopy is a powerful technique for studying weakly bound complexes formed between aromatic/heteroaromatic rings and other small molecules. However, there have been limited studies on binary or ternary clusters formed between alkyl-substituted heteroaromatic rings and water. The rotational spectrum of 2-ethylthiazole, 2-ethylthiazole···H 2 O and 2-ethylthiazole···(H 2 O) 2 have been recorded and assigned for the first time using chirped pulse Fourier transform (CP-FTMW) spectroscopy over the frequency range 2-18.5 GHz with the aid of quantum chemical calculations. Potential energy scans performed at several different levels of theory consistently predict one minimum, in which the methyl group of the ethyl side chain is orientated out of the plane defined by the thiazole ring. Experiments performed using argon and neon as carrier gases revealed that only one conformation of this molecule was present within the supersonic expansion, which is consistent with the predictions of quantum chemical calculations. However, this differs from what was previously observed in a microwave spectroscopy study of 2-ethylfuran, 1 in which two conformers of this molecule were assigned. In total, the spectra of six isotopologues of 2-ethylthiazole were assigned, 13 C and 34 S analogues were observed in natural abundance. A partial r s structure determination of this molecule allowed the determination of the tilt angle of the ethyl group. The spectra of the mono- and dihydrate complexes of 2-ethylthiazole were also assigned. In total, the spectra of six isotopologues of the monohydrate complex and three isotopologues of the dihydrate have been assigned. Non-covalent interactions (NCI) and natural bond orbital (NBO) analyses have been performed to provide an insight into the interactions present within each complex. In addition to the relatively strong hydrogen bonds within both complexes, the analyses predicted water will interact with the ethyl group. The position and relative orientation of the water molecule(s) within each complex have been determined through the calculation of intermolecular bond distances and bond angles. Parameters calculated will be compared with similar complexes 2,3 such as thiazole···H 2 O and thiazole···(H 2 O) 2 to evaluate the effect of ethyl-substitution. References 1. H. V. L. Nguyen, J. Mol. Struct. , 2020, 1208 , 127909 2. W. Li, J. Chen, Y. Xu, T. Lu, Q. Gou and G. Feng, Spectrochim. Acta, Part A , 2020, 242 , 118720 3. E. Gougoula, C. N. Cummings, Y. Xu, T. Lu, G. Feng and N. R. Walker, J. Chem. Phys ., 2023, 158 , 114307

P09

Using chemical kinetics models to unravel the origin of excess carbon and lack of nitrogen in planet-forming environments Javiera Diaz Berrios, Catherine Walsh University of Leeds, UK The material available in the planet-forming disks of dust and gas that surround young stars will determine the atmospheric composition of planets. The chemistry of these disks is diverse and is governed by gas-phase kinetics, surface reactions on dust grains, and the coupling between the two via adsorption and desorption. Thus, these disks have a rich chemistry, with more than 20 molecules detected in disks to date [1]. Because of the importance of the composition of these regions for planet formation, it is crucial to understand what processes and chemical reactions are occurring in these sources. To do this, it is necessary to constrain the abundance and distribution of organic volatiles in the planet-forming regions of disks formed from the main carriers of carbon, oxygen, nitrogen, and sulphur [2,3]. Previous observations of planet-forming disks around low-mass stars using the Spitzer Space Telescope hinted at a rich chemistry of small organic volatiles in the inner regions of the disks [4]. Motivated by these results, chemical kinetics models were developed to study the abundance and distribution of small organic molecules in disks around stars of different spectral type: M-dwarfs (Mstar=0.1Msun), T Tauri (0.5Msun) and Herbig Ae (2Msun) stars. These simulations predicted that the small organic molecules, C 2 H 2 and HCN, are more abundant in disks around low-mass stars than around higher-mass stars [5], in agreement with the observations available at that time. With the release of JWST (James Webb Space Telescope), observing the inner region of the planet-forming environment around young stars at high sensitivity and spectral resolution is now possible. JWST observations of the composition of the disk around the low-mass star J160532 (0.14Msun; [6]) revealed a planet-forming region rich in hydrocarbons (e.g., C 2 H 2 , C 4 H 2 , and C 6 H 6 ) and devoid of nitrogen carriers (e.g., NH 3 ), in contrast with predictions from chemical kinetics models [5]. The lack of NH3 in the inner regions of disks is a particular puzzle as it is predicted to be abundant in models [7]. To understand why the models are not fully consistent with observations, we employ chemical kinetics models using the physical structure of a planet-forming disk around an M-dwarf star and compute the abundances of key volatiles in the inner disk. We present results from models in which we test different radial and vertical distributions of elemental abundances (C, O, and N), thereby tuning the amount of carbon, oxygen, and nitrogen in the disk to better reproduce current observations. Processes in the disk, such as dust grain growth, settling, and drift, can drastically alter the elemental ratios in the gas and available for chemistry. We use the results of these models to determine the origin of the rich hydrocarbon chemistry and the corresponding lack of ammonia in the planet-forming regions around low-mass stars. References 1. McGuire+2022, ApJS, 259, 30

2. Pontoppidan+2014, PPVI 3. Oberg+2021, PhR, 893, 1 4. Pascucci,+2013, ApJ, 779, 178 5. Walsh+2015, A&A, 582, A88 6. Tabone+2023, NatAstron 7, 805–814 7. van Dishoeck+2023, FaradayDiscuss

P10

Spatial and temporal detection of ions ejected from Coulomb crystals using Timepix3 Jake Diprose, Vincent Richardson, Paul Regan, Adam Roberts, Sergey Burdin, Andriana Tsikritea, Brianna Heazlewood Department of Physics, University of Liverpool, UK Coulomb crystals provide a convenient environment to study ion—molecule reactions under cold and controlled conditions.[1-2] In order to better understand the content of Coulomb crystals, the fluorescence of the laser-cooled species is monitored using a charge-coupled device (CCD) camera and time-of-flight methods are used to identify and quantify the number of trapped ions. At the University of Liverpool, a phosphor-screen and microchannel plate (MCP) detector are employed in conjunction with a Timepix3 camera to spatially and temporally analyse Coulomb crystals. Timepix3 provides nanosecond resolution detection of pixels highlighted on the phosphor screen when ions hit the MCPs,[3] enabling the differentiation between ions arriving at different times on the detector. Here results are presented of Ca + /Kr + /H 2 O + multicomponent Coulomb crystals analysed using Timepix3, compared against the trapped ion structures obtained from CCD images and Coulomb crystal molecular dynamics simulations. Through analysis of the electric fields and ion trajectories using SIMION, the Timepix3 detection technique enables direct observation of fluorescent and non-fluorescent ions with Coulomb crystals. In addition, comparison of SIMION and experimental measurements highlighted how different trapping parameters, ejection fields and crystal sizes all affect ion flights and positions on the detector. Of particular note is of the effect of ejection fields, where the method of transfer from trapping to repeller and extractor fields can strongly influence the spatial distribution of the ions on the detector. In summary, we have used a combination of complementary detection methods to probe the spatial distribution of different ionic species in ejected Coulomb crystals. These findings are important, as non-laser-cooled species cannot be directly observed with a CCD camera. References 1. B. R. Heazlewood, & H. J. Lewandowski., “Chemistry Using Coulomb Crystals. Emerging Trends in Chemical Applications of Lasers” 389-410 (2021) 2. A. Tsikritea et al., “Charge transfer reactions between water isotopologues and Kr+ ions” ACS Physical Chemistry Au, 2, 3, 199-205 (2022) 3. T. Poikela., “Timepix3: a 65K channel hybrid pixel readout chip with simultaneous ToA/ToT and sparse readout” Journal of instrumentation, 9, 05, C05013 (2014)

P11

Versatile ion current rectifying nanopipette sensors for biological (pathogenic DNA) and non-biological (pesticide) molecule detection Pallavi Dutta, Shekemi Denuga, Robert P. Johnson University College Dublin, Ireland Synthetic, conical nanopore systems like nanopipettes exhibit Ion Current Rectification (ICR), a phenomenon which is highly dependent on interfacial charge. Nanopipettes are thus highly appealing for use as sensors. ICR is characterized by an asymmetric diode-like current-voltage response, where the current recorded at one voltage polarity is higher than the current recorded at the same voltage of opposite polarity 1 . The measured current is affected by both the asymmetric geometry and interfacial charges of the nanopore. Subjecting these systems to a solution of electrolyte results in the formation of an electric double layer (EDL) whose thickness is defined by Debye length and is inversely proportional to concentration. Understanding the effect of electrolyte concentration on ICR is vital for the development and optimization of nanopore sensors 2 . Functionalizing nanopipettes with biorecognition agents on the pore surfaces such as antibodies and nucleic acids can be used to detect various analytes with high sensitivity 3 . The work presented herein successfully demonstrates the viability of an ICR based nanopore sensor that can detect both biological ( MRSA DNA ) and non-biological molecules ( Imidacloprid- Pesticide ). A probe DNA-functionalized nanopipette detected the complementary target DNA exposed to it. This provides proof of concept that ICR can be utilised for the development of sensitive and specific biosensors for pathogenic DNA. Building from this knowledge pipettes functionalised with aptamers were used to create sensors for imidacloprid detection. References 1. White, H. S.; Bund, A., Ion Current Rectification at Nanopores in Glass Membranes. Langmuir 2008, 24 (5), 2212-2218. 2. Duleba, D.; Dutta, P.; Denuga, S.; Johnson, R. P., Effect of Electrolyte Concentration and Pore Size on Ion Current Rectification Inversion. ACS Measurement Science Au 2022 . 3. Zhang, S.;, Chen, W.;, Song, L.; Wang, X.; Sun, W.; Song, P.; Ashraf, G.; Liu, B.; Zhao, Y.; Recent advances in ionic current rectification based nanopore sensing: a mini-review, Sensors and Actuators Reports, Volume 3, 2021.

P12

Exploring the complex chemistry of biomass burning emissions Rhianna L. Evans 1 , Rubén Soler 2 , Teresa Vera 2 , Mila Ródenas 2 , Esther Borrás 2 , Tatiana Gómez 2 , Amalia Muñoz 2 , Andrew R. Rickard 1,3 1 Department of Chemistry, University of York, UK, 2 Instituto Universitario Centro de Estudios Ambientales del Mediterráneo (CEAM-UMH), Valencia, Spain, 3 National Centre for Atmospheric Science, University of York, UK The World Health Organisation (WHO) estimates 99% of the global population breathes air which exceeds air quality guidelines. Biomass burning, which encompasses wildfires, agricultural burning, and domestic combustion, releases large quantities of organic carbon to the atmosphere. Once emitted, the photochemical oxidation of biomass burning volatile organic compounds (BBVOCs) produces harmful secondary pollutants such as ozone (O 3 ) and secondary organic aerosol (SOA). With rapidly increasing global temperatures, the frequency of wildfires is predicted to be exacerbated by climate change resulting in poorer air quality. Some of the most reactive BBVOCs are oxygenated aromatic compounds such as phenolic and furanic species, previously identified as important precursors to SOA. Atmospheric chamber experiments can be used to study how these compounds react in the atmosphere. Many previous chamber studies have examined the chemistry of individual BBVOCs in dark or light conditions, equivalent to nighttime and daytime reactivity respectively, but few have observed the transition of chemical regime between day and night. A series of outdoor simulation chamber experiments were conducted at the EUropean PHOtoREactor (EUPHORE) in Valencia, Spain during May 2023 to replicate the night-to-day reactivity transitions of 4 BBVOCs: guaiacol, catechol, 2-methylfuran and furfural. This work aimed to understand the atmospheric chemical mechanisms of BBVOCs and observe any compositional changes between daytime and nighttime SOA which could thereby impact on toxicity. Analysis of the guaiacol experiments showed it reacted with nitrate radicals to form nitro-guaiacol during the night which subsequently decayed photochemically in the day. This indicates nitro-guaiacol chemistry is therefore important for daytime SOA and O 3 production. Concentrations of products, such as nitro-catechol and 2-methoxy- p-benzoquinone increased more rapidly in the day compared to the night suggesting reactions with daytime oxidants as major formation pathways. Overall, this work provides important mechanistic updates to BBVOC atmospheric chemistry for inclusion into air quality and climate models.

P13

Probing anomalous underscreening with a protic ionic liquid between charged interfaces Y.K. Catherine Fung, Susan Perkin Physical and Theoretical Chemistry Laboratory, University of Oxford, UK The vast possibilities presented by ionic liquids enables them to have diverse applications in areas such as solvent extraction, energy storage, and carbon dioxide capture. Despite the increasing interest in their applications, their properties, in particular, their electrical properties near charged interfaces, are not well understood. An anomalous long-range interaction which deviates from the predictions of the Debye-Hückel theory, has been observed in concentrated electrolytes (termed underscreening), including in ionic liquids. In order to probe the character of these long-range interactions, we present surface forces measurements across thin films of a protic ionic liquid, ethylammonium nitrate, at different concentrations in water between mica surfaces. These results are important for understanding the physics of concentrated electrolytes and aid the interpretation of the anomalous underscreening. References 1. M. Gebbie et al. , Proceedings of the National Academy of Sciences, 2015, 112 , 7432 2. N. Hjalmarsson et al. , Chemical Communications, 2017 , 53, 647

3. A.M. Smith et al. , The Journal of Physical Chemistry Letters, 2016 , 7, 2157 4. S. Kumar et al. , Journal of Colloid and Interface Science, 2022 , 622, 819 5. R. Horn et al. , The Journal of Physical Chemistry, 1988 , 92, 3531

P14

Application of laser flash photolysis combined with time-resolved broadband UV absorption spectroscopy to measure the total OH radical reactivity Midhun George, Dr Lisa K. Whalley, Prof Dwayne E. Heard, Dr Mark A. Blitz, Dr Daniel Stone School of Chemistry, University of Leeds, UK The composition of the atmosphere is controlled by the emission rates and chemistry of trace species emitted into the atmosphere from a wide range of sources including industry, vehicle exhausts and plants. Emissions of nitrogen oxides and volatile organic compounds (VOCs) into the atmosphere lead to complex cascades of chemical reactions which are predominantly initiated by naturally occurring OH radicals. This chemistry results in the generation of secondary pollutants such as ozone (O 3 ) and secondary organic aerosol (SOA), which impact the climate and are harmful to human health. However, it is only possible to identify and measure the concentrations of a small fraction of the vast array of over 10,000 different atmospheric VOCs, which limits our ability to provide accurate assessments and predictions of air quality. Despite such challenges, it is possible to quantify the presence and impacts of unmeasured species in the atmosphere. Since most species emitted into the atmosphere react with OH radicals, measurements of the total loss rate of OH radicals in ambient air provides a means to quantify the presence of unmeasured species, and the extent to which they contribute to the production of O 3 and SOA. Such measurements of the total OH loss rate are used to define the OH reactivity (k OH ), which can be considered to represent the total loading of reactive pollutants in an air mass that oxidise to secondary pollutants. However, routine and long-term measurements of OH reactivity are hindered by a lack of suitable techniques. In this work, a novel field instrument based on laser flash photolysis coupled with time-resolved broadband UV absorption spectroscopy has been developed and characterised for long-term measurements of k OH . The poster will present the main results from the model and experimental studies conducted during the development and characterisation of the instrument. Preliminary results from field measurements will also be presented.

P15

Unravelling the photochemical pathways for aqueous p-nitrophenol excited by 320 nm ultraviolet radiation Deborin Ghosh 1 , Nicholas Lau 2 , Min-Hsien Kao 1 , William Whitaker 1 , Ian P. Clark 3 Partha Malakar 3 , Sandra Gómez 2 , Graham A. Worth 2 , Thomas A.A. Oliver 1 , Helen H. Fielding 2 , A.J. Orr-Ewing 1 1 School of Chemistry, University of Bristol, UK, 2 Department of Chemistry, University College London, UK, 3 Central Laser Facility, Research Complex at Harwell, UK Early-time dynamics of nitroaromatics and their corresponding bases can give valuable insights into photo- induced reactions relevant to atmospheric and environmental processes. In this work, femtosecond transient broadband infra-red and electronic absorption spectroscopy have been applied to explore the ultrafast dynamics of a tropospherically important organic compound p-nitrophenol in aqueous media of different pHs. After excitation to the lowest electronically excited state, transient electronic and IR absorption spectra were recorded between 350 to 900 nm and 1400 cm -1 to 1800 cm -1 respectively for delay times from sub-picosecond up to several microseconds. Several excited state dynamics have been monitored in our experiment and their kinetics have been quantitatively measured. After rapid (~10 ps) intersystem crossing from the S 1 excited state to the triplet manifold, the p-nitrophenol (T 1 ) state decays by excited-state proton transfer (ESPT) to the surrounding water. The resulting p-nitrophenolate anion builds up in its ground electronic state (S 0 ) over a ~5 ns timescale controlled by the ESPT and subsequent relaxation of the anion from an excited triplet state. Under neutral or acidic conditions, the p-nitrophenolate (S0) is re-protonated to recover p-nitrophenol in its electronic ground state with close to 100% efficiency. The observed photochemical behaviour of the p-nitrophenolate anion in aqueous and non-aqueous media agrees with prior work by Michenfelder et al.. 1 The experimental observations help to explain why nitroaromatic compounds such as p-nitrophenol are resistant to photo-oxidative degradation in the environment. References 1. 1.N. C. Michenfelder, H. A. Ernst, C. Schweigert, M. Olzmann, A.-N. Unterreiner, Phys. Chem. Chem. Phys. 20 , 10713 (2018).

P16

Theoretical design rules for tailoring organic chromophore spectra for optoelectronic applications

James Green 1 , Eric G. Fuemmeler 2 , Timothy J. H. Hele 1 1 University College London, UK, 2 Cornell University, USA

Predicting new molecules with desirable properties for applications in organic solar cells and OLEDs is a major challenge due to the size of chemical space and the cost of electronic structure calculations. We address this by applying perturbation theory, intensity borrowing theory and electronic structure theory to the visible absorption of molecular chromophores resulting in a set of design rules for tailoring their spectra for optoelectronic applications. We then illustrate the effectiveness of this predictive tool for the case of increasing the visible absorption of acenes. We also suggest how this approach may be integrated into large-scale search methods such as high- throughput virtual screening and genetic algorithms for the rapid discovery of molecular chromophores. References 1. J D Green, E G Fuemmeler and T J H Hele, Chem. Phys. 156, 180901 (2022).

P18

A world of probabilities: an sMD/MSM approach for rational design of allosteric modulators A. Hardie 1 , B. P. Cossins 2 , S. Lovera 3 , J. Michel 1 1 School of Chemistry, University of Edinburgh, UK, 2 UCB Pharma, UK, 3 UCB Pharma, Belgium Currently it is challenging to predict whether ligands binding to an orthosteric site could be elaborated into allosteric modulators, as in these cases binding does not necessarily translate into a functional effect. We propose a workflow using steered molecular dynamics simulations (sMD) together with Markov State Models (MSM), to assess the allosteric effect of known binders. Steered MD simulations are employed to sample protein conformational space inaccessible to routine equilibrium MD timescales. Protein conformations sampled by sMD provide starting points for “seeded” molecular dynamics simulations, which are used to build an ensemble of MSMs. State probabilities computed from these MSMs may be used to predict the effect of ligand binding on protein function. The potential and challenges of applying this methodology is illustrated using case studies with Protein Tyrosine Phosphatase 1B (PTP1B) and Exchange Factor Directly Activated by cAMP (EPAC) proteins. We show that the sMD/MSM protocol correctly captures the inhibition by experimentally validated inhibitors of PTP1B and the activation of EPAC by cAMP. Additionally, nuance in defining protein “states” is discussed. These examples confirm the workflow can be used for progressing hits towards lead molecules in computer-aided drug design campaigns. References 1. A. Hardie, B. P. Cossins, S. Loverra, and J.Michel, ChemRxiv, 2023, 10.26434/chemrxiv-2023-qwhz1 2. J.-H. Prinz, H. Wu, M. Sarich, B. Keller, M. Senne, M. Held, J. D. Chodera, C. Schutte, F. Noé, J. Chem. Phys . 2011, 134

P19

Predicting NaCl morphology: are kinetic monte carlo methods enough?

John Hayton, Stephen Cox University of Cambridge, UK

A crystal’s morphology plays a vital role in determining properties such as catalytic activity. The growth processes that determine morphology, however, are only poorly understood at the molecular level. In this work, we use a recently developed kinetic Monte Carlo (KMC) approach to explore the growth of NaCl crystals at different supersaturations. We demonstrate an alchemical method for obtaining the free energies of sodium chloride lattice sites relative to a kink site, which we then use to parameterize the KMC. The resulting crystals capture some of the known morphological behaviour of NaCl, but fail to capture the shift to octahedral morphologies at higher supersaturations. Finally, we discuss possible explanations for this shortcoming, and suggest possible improvements to the model to remedy this issue.

P20

Page 1 Page 2 Page 3 Page 4 Page 5 Page 6 Page 7 Page 8 Page 9 Page 10 Page 11 Page 12 Page 13 Page 14 Page 15 Page 16 Page 17 Page 18 Page 19 Page 20 Page 21 Page 22 Page 23 Page 24 Page 25 Page 26 Page 27 Page 28 Page 29 Page 30 Page 31 Page 32 Page 33 Page 34 Page 35 Page 36 Page 37 Page 38 Page 39 Page 40 Page 41 Page 42 Page 43 Page 44 Page 45 Page 46 Page 47 Page 48 Page 49 Page 50 Page 51 Page 52 Page 53 Page 54

www.rsc.org

Made with FlippingBook Learn more on our blog