Novel correction procedure for compensating thermal contraction errors in the measurement of the magnetic field of superconducting undulator coils in a liquid helium cryostat.

Superconducting undulators (SCUs) can offer a much higher on-axis undulator field than state-of-the-art cryogenic permanent-magnet undulators with the same period and vacuum gap. The development of shorter-period and high-field SCUs would allow the free-electron laser and synchrotron radiation source community to reduce both the length of undulators and the dimensions of the accelerator. Magnetic measurements are essential for characterizing the magnetic field quality of undulators for operation in a modern light source. Hall probe scanning is so far the most mature technique for local field characterization of undulators. This article focuses on the systematic error caused by thermal contraction that influences Hall probe measurements carried out in a liquid helium cryostat. A novel procedure, based on the redundant measurement of the magnetic field using multiple Hall probes at known relative distance, is introduced for the correction of such systematic error.

Modeling the Ground- and Excited-State Unimolecular Decay of the Simplest Fluorinated Criegee Intermediate, HFCOO, Formed from the Ozonolysis of Hydrofluoroolefin Refrigerants.

Hydrofluoroolefins (HFO) are fourth-generation refrigerants designed to function as efficient refrigerants with no ozone depletion potential and zero global warming potential. Despite extensive studies on their chemical and physical properties, the ground- and excited-state chemistry of their atmospheric oxidation products is less well understood. This study focuses on the ground- and excited-state chemistry of the simplest fluorinated Criegee intermediate (CI), fluoroformaldehyde oxide (HFCOO), which is the simplest fluorinated CI formed from the ozonolysis of HFOs. HFCOO contains syn- and anti-conformers, which have Boltzmann populations of, respectively, 87 and 13% at 298 K. For both conformers, the calculated ground-state reaction energy profiles associated with cyclization to form fluorodioxirane is lower than the equivalent unimolecular decay path in the simplest CI, H2COO, with anti-HFCOO returning a barrier height more than half of that of H2COO. The excited-state dynamics reveal that photoexcitation to the bright S2 state of syn-HFCOO and anti-HFCOO is expected to undergo a prompt O-O fission─with the former conformer expected to dissociate with an almost unity quantum yield and to form both O (1D) + HFCO (S0) and O (3P) + HFCO (T1) products. In contrast, photoexcitation of anti-HFCOO is expected to undergo an O-O bond fission with a non-unity quantum yield. The fraction of photoexcited anti-HFCOO that dissociates is predicted to exclusively form O (1D) + HFCO (S0) products, which is in sharp contrast to H2COO. The wider implications of our results are discussed from both physical and atmospheric chemistry perspectives.

A direct dynamics study of the exotic photochemistry of the simplest Criegee intermediate, CH2OO.

Criegee intermediates are amongst the most fascinating molecules in modern-day chemistry. They are highly reactive intermediates that find vital roles that range from atmospheric chemistry to organic synthesis. Their excited state chemistry is exotic and complicated, and a myriad of electronic states can contribute to their photodissociation dynamics. This article reports a multi-state direct dynamics (full-dimensional) study of the photoinduced fragmentation of the simplest Criegee intermediate, CH2OO, using state-of-the-art MS-CASPT2 trajectory surface hopping. Following vertical excitation to the strongly absorbing S2(1ππ*) state, internal conversion, and thus changes in the electronic state character of the separating O + CH2O fragments, is observed between parent electronic states at separations that, traditionally, might be viewed as the classically asymptotic region of the potential energy surface. We suggest that such long-range internal conversion may account for the unusual and non-intuitive total kinetic energy distribution in the O(1D) + CH2O(S0) products observed following photoexcitation of CH2OO. The present results also reveal the interplay between seven singlet electronic states and dissociation to yield the experimentally observed O(1D) + CH2O(S0) and O(3P) + CH2O(T1) products. The former (singlet) products are favored, with a branching ratio of ca. 80%, quantifying the hitherto unknown product branching ratios observed in velocity map imaging experiments. To the best of our knowledge, such long-range internal conversions that lead to changes in the electronic state character of the fragment pairs originating from a common parent - at classically asymptotic separations - have not been recognized hitherto in the case of a molecular photodissociation.

Modeling the Conformer-Dependent Electronic Absorption Spectra and Photolysis Rates of Methyl Vinyl Ketone Oxide and Methacrolein Oxide.

Criegee intermediates are important atmospheric oxidants, formed via the reaction of ozone with volatile alkenes emitted into the troposphere. Small Criegee intermediates (e.g., CH2OO and CH3CHOO) are highly reactive, and their removal via unimolecular decay or bimolecular chemistry dominates their atmospheric lifetimes. As the molecular complexity of Criegee intermediates increases, their electronic absorption spectra show a bathochromic shift within the solar spectrum relevant to the troposphere. In these cases, solar photolysis may become a competitive contributor to their atmospheric removal. In this article, we report the conformer-dependent simulated electronic absorption spectra of two four-carbon-centered Criegee intermediates, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide). Both MVK-oxide and MACR-oxide contain four low-energy conformers, which are convoluted in the experimentally measured spectra. Here, we deconvolute each conformer and estimate contributions from each of the four conformers to the experimentally measured spectra. We also estimate the photolysis rates and predict that solar photolysis should be a more competitive removal process for MVK-oxide and MACR-oxide (cf. CH2OO and CH3CHOO).

The states that hide in the shadows: the potential role of conical intersections in the ground state unimolecular decay of a Criegee intermediate.

Criegee intermediates are of great significance to Earth's troposphere - implicated in altering the tropospheric oxidation cycle and in forming low volatility products that typically condense to form secondary organic aerosols (SOAs). As such, their chemistry has attracted vast attention in recent years. In particular, the unimolecular decay of thermal and vibrationally-excited Criegee intermediates has been the focus of several experimental and computational studies, and it is now recognized that Criegee intermediates undergo unimolecular decay to form OH radicals. In this contribution we reveal insight into the chemistry of Criegee intermediates by highlighting the hitherto neglected multi-state contribution to the ground state unimolecular decay dynamics of the Criegee intermediate products. The two key intermediates of present focus are dioxirane and vinylhydroperoxide - known to be active intermediates that mediate the unimolecular decay of CH2OO and CH3CHOO, respectively. In both cases the unimolecular decay path encounters conical intersections, which may play a pivotal role in the ensuing dynamics. This hitherto unrecognized phenomenon may be vital in the way in which the reactivity of Criegee intermediates are modelled and is likely to affect the ensuing dynamics associated with the unimolecular decay of a given Criegee intermediate.

A Simple and Efficient Method for Simulating the Electronic Absorption Spectra of Criegee Intermediates: Benchmarking on CH2OO and CH3CHOO.

Criegee intermediates (CIs) play a vital role in the atmosphere-known most prominently for enhancing the oxidizing capacity of the troposphere. Knowledge of their electronic absorption spectra is of vital importance for two reasons: (1) to aid experimentalists in detecting CIs and (2) in deciding if their removal is affected by solar photolysis. In this article we report a simple and efficient method based on the nuclear ensemble method that may be effectively used to compute the electronic absorption spectra of Criegee intermediates without the need for extensive computation of preparing the initial configurations of the starting geometry. We use this method to benchmark several excited-state electronic structure methods and their efficacy in reproducing the electronic absorption spectra of two well-known cases of CI: CH2OO and CH3CHOO. The success and computational feasibility of the methodology are crucial for its applicability to CIs of increasing molecular complexity, which have no known experimentally measured electronic absorption spectra, allowing a guide for experimentalists. Application of the methodology to more complex CIs (e.g., those with extended conjugation or those derived from endocyclic alkenes) will also reveal if solar photolysis becomes a competitive removal process when compared to unimolecular decay or bimolecular chemistry.

Photodissociation Dynamics of CH2OO on Multiple Potential Energy Surfaces: Experiment and Theory.

UV excitation of the CH2OO Criegee intermediate across most of the broad span of the (B 1A')-(X 1A') spectrum results in prompt dissociation to two energetically accessible asymptotes: O (1D) + H2CO (X 1A1) and O (3P) + H2CO (a 3A''). Dissociation proceeds on multiple singlet potential energy surfaces that are coupled by two regions of conical intersection (CoIn). Velocity map imaging (VMI) studies reveal a bimodal total kinetic energy release (TKER) distribution for the O (1D) + H2CO (X 1A1) products with the major and minor components accounting for ca. 40% and ca. 20% on average of the available energy (Eavl), respectively. The unexpected low TKER component corresponds to highly internally excited H2CO (X 1A1) products accommodating ca. 80% of Eavl. Full dimensional trajectory calculations suggest that the bimodal TKER distribution of the O (1D) + H2CO (X 1A1) products originates from two different dynamical pathways: a primary pathway (69%) evolving through one CoIn region to products and a smaller component (20%) sampling both CoIn regions enroute to products. Those that access both CoIn regions likely give rise to the more highly internally excited H2CO (X 1A1) products. The remaining trajectories (11%) dissociate to O (3P) + H2CO (a 3A'') products after traversing through both CoIn regions. The complementary experimental and theoretical investigation provides insight on the photodissociation of CH2OO via multiple dissociation pathways through two regions of CoIn that control the branching and energy distributions of products.

Photodissociation dynamics of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis.

The electronic spectrum of methyl vinyl ketone oxide (MVK-oxide), a four-carbon Criegee intermediate derived from isoprene ozonolysis, is examined on its second π* ← π transition, involving primarily the vinyl group, at UV wavelengths (λ) below 300 nm. A broad and unstructured spectrum is obtained by a UV-induced ground state depletion method with photoionization detection on the parent mass (m/z 86). Electronic excitation of MVK-oxide results in dissociation to O (1D) products that are characterized using velocity map imaging. Electronic excitation of MVK-oxide on the first π* ← π transition associated primarily with the carbonyl oxide group at λ > 300 nm results in a prompt dissociation and yields broad total kinetic energy release (TKER) and anisotropic angular distributions for the O (1D) + methyl vinyl ketone products. By contrast, electronic excitation at λ ≤ 300 nm results in bimodal TKER and angular distributions, indicating two distinct dissociation pathways to O (1D) products. One pathway is analogous to that at λ > 300 nm, while the second pathway results in very low TKER and isotropic angular distributions indicative of internal conversion to the ground electronic state and statistical unimolecular dissociation.

Oxidative Addition of Singlet Oxygen to Model Building Blocks of the Aerucyclamide A Peptide: A First-Principles Approach.

Singlet oxygen (1O2) is a significant source of biodamage in living organisms. 1O2 is a highly reactive excited electronic-state spin-configuration of molecular oxygen and is usually prepared via organic molecule sensitization. Despite the wealth of experimental studies on the 1O2-induced oxidation of several bio-organic molecules, the detailed mechanism of the oxidation process is largely unknown. Using high-level quantum chemical methods, we compute the potential energy profiles of the various electronic states associated with the [4 + 2]-cycloaddition reaction of O2 with a class of model peptide precursors that are based on derivatives of oxazole and thiazole. Experiments have shown that such oxazole/thiazole-based model peptides show a favorable reaction with 1O2. Upon increasing the molecular complexity, the bimolecular rate constant decreases and is attributed to the π-perturbing effects of the substituent of the oxazole/thiazole moiety. Our theoretical predictions are in excellent agreement with the experimental measurements and reveal a deep insight into the myriad electronic states that may hinder/promote the reaction of a given bio-organic molecule with 1O2.

Synthesis, Electronic Spectroscopy, and Photochemistry of Methacrolein Oxide: A Four-Carbon Unsaturated Criegee Intermediate from Isoprene Ozonolysis.

Ozonolysis of isoprene, one of the most abundant volatile organic compounds in the earth's atmosphere, generates the four-carbon unsaturated methacrolein oxide (MACR-oxide) Criegee intermediate. The first laboratory synthesis and direct detection of MACR-oxide is achieved through reaction of photolytically generated, resonance-stabilized iodoalkene radicals with oxygen. MACR-oxide is characterized on its first π* ← π electronic transition using a ground-state depletion method. MACR-oxide exhibits a broad UV-visible spectrum peaked at 380 nm with weak oscillatory structure at long wavelengths ascribed to vibrational resonances. Complementary theory predicts two strong π* ← π transitions arising from extended conjugation across MACR-oxide with overlapping contributions from its four conformers. Electronic promotion to the 11ππ* state agrees well with experiment, and results in nonadiabatic coupling and prompt release of O 1D products observed as anisotropic velocity-map images. This UV-visible detection scheme will enable study of its unimolecular and bimolecular reactions under thermal conditions of relevance to the atmosphere.

Exploring Norrish type I and type II reactions: an ab initio mechanistic study highlighting singlet-state mediated chemistry.

Norrish reactions are important photo-induced reactions in mainstream organic chemistry and are implicated in many industrially and biologically relevant processes and in the processing of carbonyl molecules in the atmosphere. The present study reports multi-reference electronic structure calculations designed to assess details of the potential energy profiles associated with the Norrish type-I and type-II reactions of a prototypical ketone 5-methyl-hexan-2-one. We show that the well-established 'triplet state mediated' reaction pathways following initial population of a singlet excited state can be complemented by (hitherto rarely recognized) 'singlet state only' Norrish type-I and type-II reaction mechanisms that involve no spin-forbidden transitions along the respective reaction paths, and suggest how the efficiencies of such reactions might be affected by strategic substitutions at selected sites within the parent ketone.

Mechanistic insights into photoinduced damage of DNA and RNA nucleobases in the gas phase and in bulk solution.

DNA/RNA photohydrates represent a class of well-known biomolecular lesions formed by the absorption of near- to mid-UV light. They are formed via a photoinduced nucleophilic hydrolysis reaction in which water is split (via nucleobase sensitisation) into H + OH radicals. These nascent radicals can then add across C5[double bond, length as m-dash]C6, saturating the preexisting double bond. If unrepaired, such lesions can lead to mutagenic carcinogenesis, which is responsible for several forms of cancer. Using high-level electronic structure theory (CASPT2), we map the key excited-state reaction paths associated with the reactivity of DNA (guanine and thymine) and RNA (uracil) nucleobases with water. At the outset, we consider the intrinsic reactivity in the isolated gas phase - in which the water (cluster) + chromophore complex is free from environmental perturbations. We then extrapolate the thymine nucleobase to the bulk DNA environment in aqueous solution in order to ascertain the relative importance of hydrate formation in a more complex biological environment. In this latter study we use high-level mixed quantum/classical (QM/MM: CASPT2/AMBER) methods.

Origins of Photodamage in Pheomelanin Constituents: Photochemistry of 4-Hydroxybenzothiazole.

4-Hydroxybenzothiazole (4-HBT) is a molecular constituent of pheomelanin-a polymeric skin centered pigment which acts as a natural photoprotector against harmful solar-UV radiation. Its molecular structure is therefore required to sustain a degree of photostability upon electronic excitation with UV irradiation. Despite its function as a protector against UV, pheomelanin is known to be less photostable than that of its close derivative eumelanin-a dark skin centered pigment. The 4-HBT subunit has long being attributed as a key contributor to the lack of photostability of pheomelanin-a hypothesis which we aim to test in this paper. Using high-level multireference computational methods, coupled with on-the-fly surface-hopping molecular dynamics, we find excited state reaction paths that show potential detriment to 4-HBT, leading to phototoxic radicals and products that are distinct from the original ground state molecule. Such radicals and photoproducts include those formed by classic πσ* photodissociations, intramolecular proton-transfer, and ring-opening reactions. Such reactions shed light on the types of molecular structure that show photodetrimental effects upon UV irradiation, allowing judicious predictions for synthetic analogues that may offer enhanced photoprotection in commercial sunscreens.

Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis.

Ozonolysis of isoprene, one of the most abundant volatile organic compounds in the atmosphere, proceeds through methyl vinyl ketone oxide (MVK-oxide), methacrolein oxide, and formaldehyde oxide (CH2OO) Criegee intermediates. The present study focuses on MVK-oxide, a four-carbon unsaturated carbonyl oxide intermediate, using vacuum ultraviolet photoionization at 118 nm and UV-visible induced depletion of the m/z = 86 mass channel to characterize its first π* ← π electronic transition. The electronic spectrum is broad and unstructured with its peak at 388 nm (3.2 eV). The MVK-oxide spectrum is shifted to a significantly longer wavelength than CH2OO and alkyl-substituted Criegee intermediates studied previously due to extended conjugation across the vinyl and carbonyl oxide groups. Electronic excitation results in rapid dissociation at λ ≤ 430 nm to methyl vinyl ketone and O 1D products, the latter detected by 2 + 1 resonance enhanced multiphoton ionization using velocity map imaging. Complementary electronic structure calculations (CASPT2(12,10)/AVDZ) predict two π* ← π transitions with significant oscillator strength for each of the four conformers of MVK-oxide with vertical excitation energies (and corresponding wavelengths) in the 3.1-3.6 eV (350-400 nm) and 4.5-5.5 eV (220-280 nm) regions. The computed electronic absorption profile of MVK-oxide, based on a Wigner distribution of ground state configurations and summed over the four conformers, is predicted to peak at 397 nm. UV-visible spectroscopy on the first π* ← π transition is shown by a combination of experiment and theory to provide a sensitive method for detection of the MVK-oxide Criegee intermediate that will enable further studies of its photochemistry and unimolecular and bimolecular reaction dynamics.

Photoprotection: extending lessons learned from studying natural sunscreens to the design of artificial sunscreen constituents.

Evolution has ensured that plants and animals have developed effective protection mechanisms against the potentially harmful effects of incident ultraviolet radiation (UVR). Tanning is one such mechanism in humans, but tanning only occurs post-exposure to UVR. Hence, there is ever growing use of commercial sunscreens to pre-empt overexposure to UVR. Key requirements for any chemical filter molecule used in such a photoprotective capacity include a large absorption cross-section in the UV-A and UV-B spectral regions and the availability of one or more mechanisms whereby the absorbed photon energy can be dissipated without loss of the molecular integrity of the chemical filter. Here we summarise recent experimental (mostly ultrafast pump-probe spectroscopy studies) and computational progress towards unravelling various excited state decay mechanisms that afford the necessary photostability in chemical filters found in nature and those used in commercial sunscreens. We also outline ways in which a better understanding of the photophysics and photochemistry of sunscreen molecules selected by nature could aid the design of new and improved commercial sunscreen formulations.

The near ultraviolet photodissociation dynamics of 2- and 3-substituted thiophenols: Geometric vs. electronic structure effects.

The near ultraviolet spectroscopy and photodissociation dynamics of two families of asymmetrically substituted thiophenols (2- and 3-YPhSH, with Y = F and Me) have been investigated experimentally (by H (Rydberg) atom photofragment translational spectroscopy) and by ab initio electronic structure calculations. Photoexcitation in all cases populates the 11ππ* and/or 11πσ* excited states and results in S-H bond fission. Analyses of the experimentally obtained total kinetic energy release (TKER) spectra yield the respective parent S-H bond strengths, estimates of ΔE(A∼-X∼), the energy splitting between the ground (X∼) and first excited (A∼) states of the resulting 2-(3-)YPhS radicals, and reveal a clear propensity for excitation of the C-S in-plane bending vibration in the radical products. The companion theory highlights roles for both geometric (e.g., steric effects and intramolecular H-bonding) and electronic (i.e., π (resonance) and σ (inductive)) effects in determining the respective parent minimum energy geometries, and the observed substituent and position-dependent trends in S-H bond strength and ΔE(A∼-X∼). 2-FPhSH shows some clear spectroscopic and photophysical differences. Intramolecular H-bonding ensures that most 2-FPhSH molecules exist as the syn rotamer, for which the electronic structure calculations return a substantial barrier to tunnelling from the photoexcited 11ππ* state to the 11πσ* continuum. The 11ππ* ← S0 excitation spectrum of syn-2-FPhSH thus exhibits resolved vibronic structure, enabling photolysis studies with a greater parent state selectivity. Structure apparent in the TKER spectrum of the H + 2-FPhS products formed when exciting at the 11ππ* ← S0 origin is interpreted by assuming unintended photoexcitation of an overlapping resonance associated with syn-2-FPhSH(v33 = 1) molecules. The present data offer tantalising hints that such out-of-plane motion influences non-adiabatic coupling in the vicinity of a conical intersection (between the 11πσ* and ground state potentials at extended S-H bond lengths) and thus the electronic branching in the eventual radical products.

The Validity and Reproducibility of the Flexicurve in the Evaluation of Cervical Spine Lordosis.

OBJECTIVE: The purpose of this study was to measure the validity and reliability of flexicurve measurements of cervical curvature in the sagittal plane in adults. METHODS: One hundred thirteen adults were assessed in the seated position with flexicurve radiographs. Two groups were measured: (1) the validity group (n = 55), and (2) the reliability group (n = 58). Both groups were subdivided into 3 subgroups according to body mass index: underweight, normal weight, and overweight. Radiographs were simultaneously taken with flexicurve molded on the cervical spine. Pearson's correlation and the root mean square error were used for the concurrent validity. The reliability of the flexicurve was assessed by 3 raters using the intraclass correlation coefficient (ICC), the standard error of the measurement (SEM), and minimal detectable change (MDC). RESULTS: For the concurrent validity, a high correlation (r = 0.570, P < .001, root mean square error = 9.8°), and excellent results were obtained for intra-rater (ICC = 0.771, P < .001, SEM = 4.4°, MDC = 8.6°) and inter-rater (ICC = 0.775, P < .001, SEM = 4.3°, MDC = 8.5°) reliability. The subgroups had different results, whereas the underweight subgroup consistently had the best results. CONCLUSION: These findings suggest that the flexicurve can be a valid instrument for evaluating the curvature of the cervical spine in the sagittal plane in adults classified according to the body mass index as underweight and normal weight. Reliable measurements were provided for its use whether by the same or different raters. The flexicurve can be recommended for use both in clinical practice and in research settings as long as the suggested protocol is followed.

Accuracy of a Radiological Evaluation Method for Thoracic and Lumbar Spinal Curvatures Using Spinous Processes.

OBJECTIVE: The purpose of this study was to assess a radiographic method for spinal curvature evaluation in children, based on spinous processes, and identify its normality limits. METHODS: The sample consisted of 90 radiographic examinations of the spines of children in the sagittal plane. Thoracic and lumbar curvatures were evaluated using angular (apex angle [AA]) and linear (sagittal arrow [SA]) measurements based on the spinous processes. The same curvatures were also evaluated using the Cobb angle (CA) method, which is considered the gold standard. For concurrent validity (AA vs CA), Pearson's product-moment correlation coefficient, root-mean-square error, Pitman- Morgan test, and Bland-Altman analysis were used. For reproducibility (AA, SA, and CA), the intraclass correlation coefficient, standard error of measurement, and minimal detectable change measurements were used. RESULTS: A significant correlation was found between CA and AA measurements, as was a low root-mean-square error. The mean difference between the measurements was 0° for thoracic and lumbar curvatures, and the mean standard deviations of the differences were ±5.9° and 6.9°, respectively. The intraclass correlation coefficients of AA and SA were similar to or higher than the gold standard (CA). The standard error of measurement and minimal detectable change of the AA were always lower than the CA. CONCLUSION: This study determined the concurrent validity, as well as intra- and interrater reproducibility, of the radiographic measurements of kyphosis and lordosis in children.

Theoretical insights into the photo-protective mechanisms of natural biological sunscreens: building blocks of eumelanin and pheomelanin.

Eumelanin (EM) and pheomelanin (PM) are ubiquitous in mammalian skin and hair--protecting against harmful radiation from the sun. Their primary roles are to absorb solar radiation and efficiently dissipate the excess excited state energy in the form of heat without detriment to the polymeric structure. EU and PM exist as polymeric chains consisting of exotic arrangements of functionalised heteroaromatic molecules. Here we have used state-of-the-art electronic structure calculations and on-the-fly surface hopping molecular dynamics simulations to study the intrinsic deactivation paths of various building blocks of EU and PM. Ultrafast excited state decay, via electron-driven proton transfer (in EU and PM) and proton-transfer coupled ring-opening (in PM) reactions, have been identified to proceed along hitherto unknown charge-separated states in EU and PM oligomers. These results shed light on the possible relaxation pathways that dominate the photochemistry of natural skin melanins. Extrapolation of such findings could provide a gateway into engineering more effective molecular constituents in commercial sunscreens--with reduced phototoxicity.

A 'bottom up', ab initio computational approach to understanding fundamental photophysical processes in nitrogen containing heterocycles, DNA bases and base pairs.

The availability of non-radiative decay mechanisms by which photoexcited molecules can revert to their ground electronic state, without experiencing potentially deleterious chemical transformation, is fundamental to molecular photostability. This Perspective Article combines results of new ab initio electronic structure calculations and prior experimental data in an effort to systematise trends in the non-radiative decay following UV excitation of selected families of heterocyclic molecules. We start with the prototypical uni- and bicyclic molecules phenol and indole, and explore the structural and photophysical consequences of incorporating progressively more nitrogen atoms within the respective ring structures en route to the DNA bases thymine, cytosine, adenine and guanine. For each of the latter, we identify low energy non-radiative decay pathways via conical intersections with the ground state potential energy surface accessed by out-of-plane ring deformations. This is followed by summary descriptions and illustrations of selected rival (electron driven H atom transfer) non-radiative excited state decay processes that demand consideration once the nucleobases are merely components in larger biomolecular systems like nucleosides, and both individual and stacked base-pairs.