Time-of-flight Distributions Research Articles

Fast neutron generation with few-cycle, relativistic laser pulses at 1 Hz repetition rate

Laser-driven deuterons generate neutrons with a mean energy of 2.5 MeV, through the 2H(d,n) fusion reaction in a deuterated polyethylene (dPE) tablet. The deuterium ions are accelerated by 12 fs, 21 mJ laser pulses interacting with a 0.2 µm thin dPE foil at a peak intensity of 1018 W/cm2. The laser was operated at 1 Hz repetition rate in bursts of 75 shots. The interaction was characterized and recorded for each laser shot. The ion spectra were measured in the forward and backward directions by Thomson ion spectrometers. Neutron events were detected by a time-of-flight (ToF) system consisting of four plastic scintillators positioned at various angles around the experimental chamber. The maximum cut-off energy of the forward accelerated protons and deuterons was close to 1.4 MeV and 1 MeV, while the mean values are 428 ± 63 keV and 433 ± 80 keV, respectively. Analysis of ToF distributions from 3128 shots resulted in an average yield of 1142 ± 59 neutrons per shot in the energy range of 1.5–4 MeV. The energy distribution of forward-directed neutrons peaks between 3 and 3.5 MeV. Angular dependence analysis showed a perpendicular minimum and a maximum along the deuteron beam, consistent with the expected distribution from the literature and our simulation results.

Pathlength-selective, interferometric diffuse correlation spectroscopy (PaLS-iDCS).

Diffuse correlation spectroscopy (DCS) is an optical method that offers non-invasive assessment of blood flow in tissue through the analysis of intensity fluctuations in diffusely backscattered coherent light. The non-invasive nature of the technique has enabled several clinical applications for deep tissue blood flow measurements, including cerebral blood flow monitoring as well as tumor blood flow mapping. While a promising technique, in measurement configurations targeting deep tissue hemodynamics, the standard DCS implementations suffer from insufficient signal-to-noise ratio (SNR), depth sensitivity, and sampling rate, limiting their utility. In this work, we present an enhanced DCS method called pathlength-selective, interferometric DCS (PaLS-iDCS), which improves upon both the sensitivity of the measurement to deep tissue hemodynamics and the SNR of the measurement using pathlength-specific coherent gain. Through interferometric detection, PaLS-iDCS can provide time-of-flight (ToF) specific blood flow information without the use of expensive time-tagging electronics and low-jitter detectors. The new technique is compared to time-domain DCS (TD-DCS), another enhanced DCS method able to resolve photon ToF in tissue, through Monte Carlo simulation, phantom experiments, and human subject measurements. PaLS-iDCS consistently demonstrates improvements in SNR (>2x) for similar measurement conditions (same photon ToF), and the SNR improvements allow for measurements at extended photon ToFs, which have increased sensitivity to deep tissue hemodynamics (~50% increase). Further, like TD-DCS, PaLS-iDCS allows direct estimation of tissue optical properties from the sampled ToF distribution without the need for a separate spectroscopic measurement. This method offers a relatively straightforward way to allow DCS systems to make robust measurements of blood flow with greatly enhanced sensitivity to deep tissue hemodynamics, enabling further applications of this non-invasive technology.

Experimental Validation of Comprehensive Calculation for High-Resolution Linear MALDI-TOF Mass Spectrometry.

This work discusses the effectiveness of the previously developed comprehensive calculation model to optimize linear MALDI-TOF mass spectrometers. The model couples space- and velocity-focusing to precisely analyze the flight-time distribution of ions and predict optimal experimental parameters for the highest mass resolving power. Experimental validation was conducted using a laboratory-made instrument to analyze CsI3 and angiotensin I ions in low to medium m/z range. The results indicate that the predicted optimal extraction voltage and delay were reasonably accurate and effective. In the low m/z range, the peak width obtained using optimal parameters reached the sub nanosecond range, corresponding to a mass resolving power of 10 000-17 000, or 20 000-34 000 if shot-to-shot random fluctuations were minimized by the dynamic data correction method. The observed optimal mass resolving power in the current experiment is 4.8-7.8 times that of commercial instruments. Practical limitations resulting in the gap between the observed and theoretical ultimate mass resolving power are discussed.

DNA Barcodes Using a Dual Nanopore Device.

We report a novel method based on the current blockade (CB) characteristics obtained from a dual nanopore device that can determine DNA barcodes with near-perfect accuracy using a Brownian dynamics simulation strategy. The method supersedes our previously reported velocity correction algorithm (S. Seth and A. Bhattacharya, RSC Advances, 11:20781-20787, 2021), taking advantage of the better measurement of the time-of-flight (TOF) protocol offered by the dual nanopore setup. We demonstrate the efficacy of the method by comparing our simulation data from a coarse-grained model of a polymer chain consisting of 2048 excluded volume beads of diameter 𝜎 = 24bp using with those obtained from experimental CB data from a 48,500bp λ-phage DNA, providing a base pair resolution in simulation. The simulation time scale is compared to the experimental time scale by matching the simulated time-of-flight (TOF) velocity distributions with those obtained experimentally (Rand et al., ACS Nano, 16:5258-5273, 2022). We then use the evolving coordinates of the dsDNA and the molecular features to reconstruct the current blockade characteristics on the fly using a volumetric model based on the effective van der Waal radii of the species inside and in the immediate vicinity of the pore. Our BD simulation mimics the control-zoom-in-logic to understand the origin of the TOF distributions due to the relaxation of the out-of-equilibrium conformations followed by a reversal of the electric fields. The simulation algorithm is quite general and can be applied to differentiate DNA barcodes from different species.

Numerical analysis of pulsed extraction of ions from a 16-Pole / 16-Wire ion trap for time-of-flight mass spectrometry

Multipole radiofrequency ion traps are versatile tools for trapping and manipulating ions. The extraction of ions from such a trap leads to broad time-of-flight (ToF) distributions, which make it incompatible with ToF mass spectrometry. In this work, we conducted numerical simulations of biomolecular ions stored in 16-pole and 16-wire ion traps to analyze their extraction characteristics. We show that the ions extracted from a wire trap with a simple upgrade exhibit ToF distributions two orders of magnitude narrower than that typically results from conventional ion traps. Further, in the upgraded design, the ions can be confined within a much narrower region, which, together with higher optical access of the wire trap configuration, makes it compatible with fluorescence spectroscopy measurements.

Potential for remote TD-NIRS imaging using a TCSPC camera

Advances in the CMOS process enables single-photon detection and timing to occur within an individual pixel. Pixel arrays incorporating this in-pixel timing methodology have been increasing in size, facilitating time of flight (ToF) imaging. This means that a fully parallel approach can be made to the collection of images, dramatically speeding up data collection in relation to sample scanning and allowing imaging based on time-correlated single-photon counting (TCSPC) to be made in real time. In this work we make use of a commercial TCSPC camera, based on an array of 192 × 126 imaging pixels with in-pixel timing applied in the area of time-domain near infrared spectroscopy. The potential of remote imaging using this methodology was demonstrated using two model systems. The effect of increasing scattering coefficient using a liquid based (milk added to water) system to assess real time potential was investigated. Additionally a more complex system consisting of a solid with liquid interior (egg) to verify the potential of remote imaging into the interior of the object with different illumination conditions was studied. Using a time-slicing approach intensity images related to each time bin in the ToF distribution were obtained and contrast between the yolk and albumin within the egg was observed.

The N(2D) + CH2CHCN (Vinyl Cyanide) Reaction: A Combined Crossed Molecular Beam and Theoretical Study and Implications for the Atmosphere of Titan.

The reaction of electronically excited nitrogen atoms, N(2D), with vinyl cyanide, CH2CHCN, has been investigated under single-collision conditions by the crossed molecular beam (CMB) scattering method with mass spectrometric detection and time-of-flight (TOF) analysis at the collision energy, Ec, of 31.4 kJ/mol. Synergistic electronic structure calculations of the doublet potential energy surface (PES) have been performed to assist in the interpretation of the experimental results and characterize the overall reaction micromechanism. Statistical (Rice–Ramsperger–Kassel–Marcus, RRKM) calculations of product branching fractions (BFs) on the theoretical PES have been carried out at different values of temperature, including the one corresponding to the temperature (175 K) of Titan’s stratosphere and at a total energy corresponding to the Ec of the CMB experiment. According to our theoretical calculations, the reaction is found to proceed via barrierless addition of N(2D) to the carbon–carbon double bond of CH2=CH–CN, followed by the formation of cyclic and linear intermediates that can undergo H, CN, and HCN elimination. In competition, the N(2D) addition to the CN group is also possible via a submerged barrier, leading ultimately to N2 + C3H3 formation, the most exothermic of all possible channels. Product angular and TOF distributions have been recorded for the H-displacement channels leading to the formation of a variety of possible C3H2N2 isomeric products. Experimentally, no evidence of CN, HCN, and N2 forming channels was observed. These findings were corroborated by the theory, which predicts a variety of competing product channels, following N(2D) addition to the double bond, with the main ones, at Ec = 31.4 kJ/mol, being six isomeric H forming channels: c-CH(N)CHCN + H (BF = 35.0%), c-CHNCHCN + H (BF = 28.1%), CH2NCCN + H (BF = 26.3%), c-CH2(N)CCN(cyano-azirine) + H (BF = 7.4%), trans-HNCCHCN + H (BF = 1.6%), and cis-HNCCHCN + H (BF = 1.3%), while C–C bond breaking channels leading to c-CH2(N)CH(2H-azirine) + CN and c-CH2(N)C + HCN are predicted to be negligible (0.02% and 0.2%, respectively). The highly exothermic N2 + CH2CCH (propargyl) channel is also predicted to be negligible because of the very high isomerization barrier from the initial addition intermediate to the precursor intermediate able to lead to products. The predicted product BFs are found to have, in general, a very weak energy dependence. The above cyclic and linear products containing an additional C–N bond could be potential precursors of more complex, N-rich organic molecules that contribute to the formation of the aerosols on Titan’s upper atmosphere. Overall, the results are expected to have a significant impact on the gas-phase chemistry of Titan’s atmosphere and should be properly included in the photochemical models.

Heterogeneous ultrasonic time-of-flight distribution in multidirectional CFRP corner and its implementation into total focusing method imaging

A precise time-of-flight (TOF) of phased array ultrasonic is crucial to the high-quality total focusing method (TFM) imaging in the corner of multidirectional carbon fiber reinforced plastics, but quite challenging owing to the complex material and geometric factors. With a comprehensive consideration of the curved shape, laminated structure, and elastic anisotropy, we propose a high-fidelity finite element model of the corner based on the stiffness matrix analysis. A strategy in virtue of the maximum energy of A-scan signals, is further implemented to determine the TOF and compared with the exiting minimum time method. The resulted heterogeneous TOF distributions are input into TFM imaging, respectively. Results show that of an isotropic approximation presents a larger positioning error and a higher noise level of defects. In contrast, the anisotropic algorithms, especially for the maximum energy method, obviously improve the defect echo amplitude and suppress the sub-surface noise, demonstrating a superior performance in CFRP characterization.

The Influence of the Symmetry of Identical Particles on Flight Times.

In this work, our purpose is to show how the symmetry of identical particles can influence the time evolution of free particles in the nonrelativistic and relativistic domains as well as in the scattering by a potential -barrier. For this goal, we consider a system of either two distinguishable or indistinguishable (bosons and fermions) particles. Two sets of initial conditions have been studied: different initial locations with the same momenta, and the same locations with different momenta. The flight time distribution of particles arriving at a ‘screen’ is calculated in each case from the density and flux. Fermions display broader distributions as compared with either distinguishable particles or bosons, leading to earlier and later arrivals for all the cases analyzed here. The symmetry of the wave function seems to speed up or slow down the propagation of particles. Due to the cross terms, certain initial conditions lead to bimodality in the fermionic case. Within the nonrelativistic domain, and when the short-time survival probability is analyzed, if the cross term becomes important, one finds that the decay of the overlap of fermions is faster than for distinguishable particles which in turn is faster than for bosons. These results are of interest in the short time limit since they imply that the well-known quantum Zeno effect would be stronger for bosons than for fermions. Fermions also arrive earlier and later than bosons when they are scattered by a -barrier. Although the particle symmetry does affect the mean tunneling flight time, in the limit of narrow in momentum initial Gaussian wave functions, the mean times are not affected by symmetry but tend to the phase time for distinguishable particles.

Theoretical study of the impact of ion acceleration parameters on the mass resolving power in linear MALDI time-of-flight mass spectrometry

This work examines how ion acceleration parameters affect the mass resolving power (Rm) of linear time-of-flight (TOF) mass spectrometry (MS). Ion acceleration parameters have been considered as playing a minor role in determining the Rm in TOF MS. Based on results in two-dimensional topological space calculated in this work, we demonstrate that the length and electrical potential of the ion acceleration region critically affect Rm. The flight-time distribution of ions of m/z 3000 in a 3-m long linear TOF mass spectrometer is analyzed using the coupled space-velocity focusing method. Big data analysis reveals that four types of flight-time distribution are available by adjusting ion acceleration length. The coefficients in the equation of flight-time spread can be used to predict the best length for achieving highest performance. The results show an 18-fold increase in Rm when increasing the length of the ion acceleration region by a factor of ∼35 with respect to conventional design. Adjusting ion extraction parameters cannot provide the same magnitude of improvement. Correlation between Rm and critical experimental parameters are discussed.

Bayesian inference of Lévy walks via hidden Markov models

The Lévy walk (LW) is a non-Brownian random walk model that has been found to describe anomalous dynamic phenomena in diverse fields ranging from biology over quantum physics to ecology. Recurrently occurring problems are to examine whether observed data are successfully quantified by a model classified as LWs or not and extract the best model parameters in accordance with the data. Motivated by such needs, we propose a hidden Markov model for LWs and computationally realize and test the corresponding Bayesian inference method. We introduce a Markovian decomposition scheme to approximate a renewal process governed by a power-law waiting time distribution. Using this, we construct the likelihood function of LWs based on a hidden Markov model and the forward algorithm. With the LW trajectories simulated at various conditions, we perform the Bayesian inference for parameter estimation and model classification. We show that the power-law exponent of the flight-time distribution can be successfully extracted even at the condition that the mean-squared displacement does not display the expected scaling exponent due to the noise or insufficient trajectory length. It is also demonstrated that the Bayesian method performs remarkably inferring the LW trajectories from given unclassified trajectory data set if the noise level is moderate.

Numerical study of transverse position monitor and compensation for x-ray polarization diagnosis.

Diagnosing free electron laser (FEL) polarization is critical for polarization-modulated research such as x-ray FEL diffraction imaging and probing material magnetism. In an electron time-of-flight (eTOF) polarimeter, the flight time and angular distribution of photoelectrons were designed based on x-ray polarimetry for on-site diagnosis. However, the transverse position of x-ray FEL pulses introduces error into the measured photoelectron angular distribution. This work, thus, proposes a method of compensating transverse position jitters for the polarization by the eTOF polarimeter itself without an external x-ray beam-position monitor. A comprehensive numerical model is developed to demonstrate the feasibility of the compensation method, and the results reveal that a spatial resolution of 20 μm and a polarity improved by 0.02 are possible with fully polarized FEL pulses. The impact of FEL pulses and a method to calibrate their linearity are also discussed.

Thermometry in a Multipole Ion Trap

We present a characterization of the ions’ translational energy distribution in a multipole ion trap. A linear mapping between the energy distribution of the trapped ions onto the ions’ time-of-flight (TOF) to a detector is demonstrated. For low ion temperatures, a deviation from linearity is observed and can be attributed to the emergence of multiple potential minima. The potential landscape of the trapped ions is modeled via the finite element method, also accounting for subtleties such as surface-charge accumulation. We demonstrate the validity of our thermometry method by simulating the energy distribution of the ion ensemble thermalized with buffer gas using a Molecular Dynamics (MD) simulation. A comparison between the energy distribution of trapped ions in different multipole trap configurations—i.e., with hyperbolic rods, cylindrical rods, and cylindrical wires—is provided. With these findings, one can map the temperature of the trapped ions down to the Kelvin regime using their TOF distributions. This enables future studies on sympathetic cooling and chemical reactions involving ions in multipole traps.

Construction of finite rate surface chemistry models from pulsed hyperthermal beam experimental data

A general approach for constructing finite rate surface chemistry models using time-of-flight (TOF) distribution data acquired from pulsed hyperthermal beam experiments is presented. First, a detailed study is performed with direct simulation Monte Carlo (DSMC) to analyze the TOF distributions corresponding to several types of reaction mechanisms occurring over a wide temperature range. This information is used to identify and isolate the products formed through different reaction mechanisms from TOF and angular distributions. Next, a procedure to accurately calculate the product fluxes from the TOF and angular distributions is outlined. Finally, in order to derive the rate constant of the reactions within the system, the inherent transient characteristic of the experimental pulsed beam set up must be considered. An analysis of the steady-state approximation commonly used for deriving the rate constants reveals significant differences in terms of the total product composition. To overcome this issue, we present a general methodology to derive the reaction rate constants, which takes into account the pulsed setup of the beam. Within this methodology, a systematic search is performed through the rate constant parameter space to obtain the values that provide the best agreement with experimentally observed product compositions. This procedure also quantifies the surface coverage that corresponds to the rates of product formation. This approach is applied to a sample system: oxidation reaction on vitreous carbon surfaces to develop a finite-rate surface chemistry model. Excellent agreement is observed between the developed model and the experimental data, thus showcasing the validity of the proposed methodologies.

Scattering Dynamics of Nitromethane and Methyl Formate on Highly Oriented Pyrolytic Graphite (HOPG)

The gas–surface scattering dynamics of nitromethane (CH3NO2) and methyl formate (HCOOCH3) on a highly oriented pyrolytic graphite (HOPG) surface have been investigated as part of a broader effort to evaluate the efficacy of a funnel-like neutral gas concentrator that has been proposed as a mass spectrometer inlet for the characterization of tenuous planetary atmospheres or plumes. Molecular beams of CH3NO2 and HCOOCH3 with incidence energies, Ei, of 106.5 and 98.8 kJ mol–1, respectively, were directed at the surface with incidence angles, θi, of 70, 45, and 30°. A rotatable mass spectrometer, employing electron-impact ionization, was used to collect angle-resolved time-of-flight (TOF) distributions of the molecules that scattered inelastically from the surface, allowing angular distributions of the scattered product flux and translational energy distributions at a given final angle, θf, to be obtained. The TOF distributions of the scattered products detected the parent ion mass-to-charge ratios and their respective dominant ion fragments were identical, indicating that CH3NO2 and HCOOCH3 fragmented in the ionizer of the detector and not while colliding with the surface. The scattering dynamics suggested that the parallel momentum of the molecules was conserved during impact with the surface. The translational energy and angular distributions of CH3NO2 and HCOOCH3 were identical when θi = 70°. For θi = 45 and 30°, the HCOOCH3 angular distributions were shifted to a slightly larger θf than the CH3NO2 distributions. The molecules scattered from the surface through impulsive scattering (IS) and quasitrapping (QT) pathways. The IS molecules retained a large fraction of their incidence translational energy when colliding with the surface. The QT molecules transferred more energy, but they did not come completely into thermal equilibrium with the surface before scattering into the vacuum. The QT molecules had a lobular angular distribution with a maximum flux far from the surface normal, indicating that they retained some memory of their incident conditions despite losing a significant amount of energy at the surface. The results presented in this article demonstrate that for Ei near 100 kJ mol–1, these molecules would not dissociate upon impact with the surfaces of a gas concentrator constructed of HOPG. Although the observed scattering dynamics suggest that such a concentrator could perform well for a variety of molecular species, accurate concentration factors are ultimately molecule-specific and determined by the details of the molecule–surface interaction potential.

Development and validation of a finite-rate model for carbon oxidation by atomic oxygen

Molecular beam experiments of hyperthermal oxygen atoms scattering from a vitreous carbon surface were simulated and analyzed using direct simulation Monte Carlo (DSMC). The purpose of this study was to construct and validate a surface chemistry model in DSMC by matching observed features in experimental time-of-flight (TOF) and angular distribution data. A variety of reaction mechanisms including adsorption, desorption, and several types of Langmuir-Hinshelwood (LH) reactions are used to characterize the surface processes in the DSMC surface chemistry framework. This framework is used to numerically simulate the beam-surface scattering experiments of oxygen on vitreous carbon with surface temperatures ranging from 600 to 2000 K. Detailed analysis of the experimental data including TOF and angular distributions, and product fluxes derived from these data, is used to propose modifications to the carbon surface oxidation model developed by Poovathingal et al. This revised model successfully captures the important features in the experimental TOF distributions, including: (i) the impulsively scattered and thermally desorbed components in the oxygen (O) TOF distributions, and (ii) the relatively slow long-tail components in the carbon monoxide (CO) TOF distributions. Comparisons between the simulated (DSMC) and experimental TOF and angular distributions, as well as product fluxes, show excellent agreement.

Implementation and Optimization of Large Gas Cluster Laser Post-Ionization Secondary Neutral Mass Spectrometry for Molecular Analysis

In this study, we describe for the first time a new combined technique for molecular surface analysis using large argon gas clusters as primary ions for laser postionization secondary neutral mass spectrometry (Laser-SNMS). This new technique was investigated on polymer polystyrene (PS) surfaces using pulsed Ar2000+ ions with 20 keV energy and a 157 nm laser beam for postionization. To optimize the ion yield, time-of-flight (ToF) distributions of characteristic sputtered neutral PS fragments were determined. The data could be fitted well with Maxwell–Boltzmann distributions. The data show that the maxima of the individual ToF distributions of the sputtered neutrals move to higher delay time values with increasing mass, which directly correlates to a decrease of velocity of the sputtered neutrals with increasing mass. The delay time dependence on mass could be fitted with a quadratic curve, thus indicating a constant mean kinetic energy for the sputtered molecules. The ion yields obtained with large gas cl...

Modelling the line shape of very low energy peaks of positron beam induced secondary electrons measured using a time of flight spectrometer

In this paper, we present results of numerical modelling of the University of Texas at Arlington’s time of flight positron annihilation induced Auger electron spectrometer (UTA TOF-PAES) using SIMION® 8.1 Ion and Electron Optics Simulator. The time of flight (TOF) spectrometer measures the energy of electrons emitted from the surface of a sample as a result of the interaction of low energy positrons with the sample surface. We have used SIMION® 8.1 to calculate the times of flight spectra of electrons leaving the sample surface with energies and angles dispersed according to distribution functions chosen to model the positron induced electron emission process and have thus obtained an estimate of the true electron energy distribution. The simulated TOF distribution was convolved with a Gaussian timing resolution function and compared to the experimental distribution. The broadening observed in the simulated TOF spectra was found to be consistent with that observed in the experimental secondary electron spectra of Cu generated as a result of positrons incident with energy 1.5 eV to 901 eV, when a timing resolution of 2.3 ns was assumed.

Can 3D light localization be reached in ‘white paint’?

When waves scatter multiple times in 3D random media, a disorder driven phase transition from diffusion to localization may occur (Anderson 1958 Phys. Rev. 109 1492–505; Abrahams et al 1979 Phys. Rev. Lett. 42 673–6). In ‘The question of classical localization: a theory of white paint?’ Anderson suggested the possibility to observe light localization in TiO2 samples (Anderson 1985 Phil. Mag. B 52 505–9). We recently claimed the observation of localization effects measuring photon time of flight (ToF) distributions (Störzer et al 2006 Phys. Rev. Lett. 96 063904) and evaluating transmission profiles (TPs) (Sperling et al 2013 Nat. Photonics 7 48–52) in such TiO2 samples. Here we present a careful study of the long time tail of ToF distributions and the long time behavior of the TP width for very thin samples and different turbidities that questions the localization interpretation. We further show new data that allow an alternative consistent explanation of these previous data by a fluorescence process. An adapted diffusion model including an appropriate exponential fluorescence decay accounts for the shape of the ToF distributions and the TP width. These observations question whether the strong localization regime can be reached with visible light scattering in polydisperse TiO2 samples, since the disorder parameter can hardly be increased any further in such a ‘white paint’ material.

Electrophoretic Transport of Single DNA Nucleotides through Nanoslits: A Molecular Dynamics Simulation Study.

There is potential for flight time based DNA sequencing involving disassembly into individual nucleotides which would pass through a nanochannel with two or more detectors. We performed molecular dynamics simulations of electrophoretic motion of single DNA nucleotides through 3 nm wide hydrophobic slits with both smooth and rough walls. The electric field (E) varied from 0.0 to 0.6 V/nm. The nucleotides adsorb and desorb from walls multiple times during their transit through the slit. The nucleotide-wall interactions differed due to nucleotide hydrophobicities and wall roughness which determined duration and frequency of nucleotide adsorptions and their velocities while adsorbed. Transient association of nucleotides with one, two, or three sodium ions occurred, but the mean association numbers (ANs) were weak functions of nucleotide type. Nucleotide-wall interactions contributed more to separation of nucleotide flight time distributions than ion association and thus indicate that nucleotide-wall interactions play a defining role in successfully discriminating between nucleotides on the basis of their flight times through nanochannels/slits. With smooth walls, smaller nucleotides moved faster, but with rough walls larger nucleotides moved faster due to fewer favorable wall adsorption sites. This indicates that roughness, or surface patterning, might be exploited to achieve better time-of-flight based discrimination between nucleotides.