Ab Initio Transition State Theory Research Articles

On non‐hydrogen‐atom products of thermal decomposition of benzyl radical: A theoretical investigation by the transition state theory/multi‐well master equation approach

AbstractBenzyl radical (C7H7), one of the resonantly stabilized hydrocarbon radicals, is one of the significant precursors of polycyclic aromatic hydrocarbons in interstellar media and combustion engines. The unimolecular decomposition of benzyl radical is still incompletely understood despite of its importance and relatively small molecular size. The decomposition reactions of benzyl radical were investigated in the present study by using the ab initio transition state theory (TST) and the multi‐well master equation theory. Specifically, all reaction pathways on the potential energy surface of C7H7 was calculated at the level of QCISD(T)/CBS. For the reactions with multireference characters, the CASPT2(9e,7o)/aug‐cc‐pVTZ method was used to calculate the vibrational frequencies and energies of structures along the one‐dimensional reaction coordinate of the breaking bond. The high‐pressure limits of rate constants for all the reactions were obtained by using the TST except those for C7H6 + H and C6H4 + CH3 by the variational TST. The pressure‐dependent rate constants were obtained by using the multi‐well master equation simulations. The calculated rate constants agree well with available experimental and theoretical data in the literature. Moreover, the present results identify the composition of the non‐hydrogen‐atom production observed in previous experiments, which provide new insights into the reactions of aromatic compounds.

Relevance of the P+O2 Reaction for PO Formation in Astrochemical Environments: Electronic Structure Calculations and Kinetic Simulations

Phosphorus monoxide (PO) is a key brick of prebiotic chemistry since it is a potential precursor of phosphates, which are present in all living systems. Prompted by the lack of information on the different processes involved in the formation of PO, we have revisited and analyzed in detail the P(4 S) + O2(3Σ−) and P(4 S) + O2(1Δ) reactions leading to PO. The former process has been widely studied from both experimental and theoretical points of view, however, with contradictory results. We have used high-level quantum-chemical calculations to accurately describe the reaction mechanisms. Next, rate constants have been computed using a master equation approach based on ab initio transition state theory. By incorporating the P(4 S) + O2(3Σ−) reaction in an astrochemical model, we have found that this reaction cannot be overlooked when aiming at a complete understanding of the PO abundance in regions dominated by shocks with speeds below 40 km s−1.

On the General Mechanism for the Gas-phase Reaction of Methanimine with a Radical Species in the Interstellar Medium: Some Failures and an Important Success

Abstract The gas-phase reactions of methanimine (CH2NH) with small radicals, such as CN, CP, CCH, and OH, have been extensively studied theoretically in the literature, and the presence of a common, general reaction mechanism has been postulated. Since methanimine is considered the main precursor of complex imines in the interstellar medium (ISM), the present study extends the investigation of its reaction with other small radicals that have already been detected in the ISM. These are SiN, SH, NO, NS, HCO, HCS, and C3N. The corresponding products are easily formulated on the basis of the aforementioned general mechanism, and to understand whether they can be formed in the ISM, a preliminary thermochemical study has been carried out. The only exothermic addition reaction is that occurring between CH2NH and the C3N radical. This reaction has been further investigated in order to accurately characterize its reactive potential energy surface, which has then been employed in ab initio transition state theory calculations to derive global rate coefficients. The products of the CH2NH + C3N reaction are new potential interstellar species, namely, the Z and E isomers of HNCHCCCN and CH2NCCCN. For the first time, their structural characterization has been reported. In addition, this work investigates the possibility of H-abstraction processes for each radical species considered, and re-examines the CH2NH + CP reaction to derive the corresponding rate constants, that were still missing in the literature.

An Ab initio based OH initiated oxidation kinetics of glycerol carbonate: A promising biofuel component

The global energy demand is steadily increasing because of the population explosion and economic growth. Fossil fuels supply around 85 % of global primary energy demand. On one hand, fulfilling the increasing energy demands is a big challenge for the next few decades. On the other hand, the continued burning of fossil fuels leads to higher CO2 emissions, severely impacting global warming. Therefore, the policymakers vow to shift from conventional fuels to renewable resources for economic, environmental, and future energy security reasons. In this context, biofuels from lignocellulosic biomass and/or carbon-neutral fuels produced in the sustainable carbon cycle can close the carbon cycle and reach net zero-carbon emission. Recently, glycerol carbonate has been proposed as a promising fuel or fuel additive for future sustainability. Therefore, we investigated the hydrogen abstraction reactions of glycerol carbonate (GC) by OH radicals using high-level ab initio and variational transition state theory calculations. We mapped out the potential energy surface using the CCSD(T)/cc-pV(D, T)Z//MP2/cc-pVTZ level of theory. We used the ab initio parameters to obtain the site-specific rate coefficients by employing the variational transition state theory. We observed that every hydrogen atom in GC displays a unique reactivity with OH radicals. We derived branching ratio of each channel that are difficult to access experimentally. The overall rate coefficients exhibit a strong non-Arrhenius behaviour, which can be represented as:kovCVT/SCT(T)=3.39×10−20×T2.659×e−750.0Jmol−1RTcm3moleculesThis is the first reported rate data for the glycerol carbonate and OH radicals reaction.

On the decomposition mechanism of propanal: rate constants evaluation and kinetic simulations

The reactivity of aldehydes has been the subject of considerable interest in chemical kinetics, with propanal often chosen as the representative species. Despite its relevance, the reactivity of propanal is currently estimated from analogy and fitting of experimental data measured in limited temperature and pressure ranges, while the few literature theoretical studies have focused more on the exploration the potential energy surface (PES) than on the estimation of rate constants. The purpose of this work is to reinvestigate the propanal decomposition kinetics using the ab initio transition state theory based master equation approach with the intent of: (1) Determining accurate rate constants of key reaction channels; (2) Updating and validating an existing kinetic model by simulating available experimental data on propanal pyrolysis. It is found that propanal decomposition at the initial stages of pyrolysis occurs through four unimolecular barrierless reactions to form CHO + C2H5, CH2CHO + CH3, CH3CHCHO + H, and CH3CH2CO + H, and a termolecular pathway leading to the formation of C2H4 + CO + H2. High pressure rate constants were determined for each barrierless reaction channel using Variable Reaction Coordinate Transition State Theory and used to estimate phenomenological temperature and pressure dependent channel specific rate constants integrating the 1 dimensional master equation over the whole PES. The decomposition rate constants so determined are in agreement with the few available experimental data and significantly faster than previous literature estimates. The estimated kinetic parameters were finally implemented into the CRECK kinetic mechanism, leading to an improved agreement with shock tube pyrolysis data from the literature.

Reliable Gas Phase Reaction Rates at Affordable Cost by Means of the Parameter-Free JunChS-F12 Model Chemistry.

A recently developed strategy for the computation at affordable cost of reliable barrier heights ruling reactions in the gas phase (junChS, [Barone, V.; J. Chem. Theory Comput. 2021, 17, 4913-4928]) has been extended to the employment of explicitly correlated (F12) methods. A thorough benchmark based on a wide range of prototypical reactions shows that the new model (referred to as junChS-F12), which employs cost-effective revDSD-PBEP86-D3(BJ) reference geometries, has an improved performance with respect to its conventional counterpart and outperforms the most well-known model chemistries without the need of any empirical parameter and at an affordable computational cost. Several benchmarks show that revDSD-PBEP86-D3(BJ) structures and force fields provide zero point energies and thermal contributions, which can be confidently used, together with junChS-F12 electronic energies, for obtaining accurate reaction rates in the framework of the master equation approach based on the ab initio transition-state theory.

Spiers Memorial Lecture: Theory of unimolecular reactions.

One hundred years ago, at an earlier Faraday Discussion meeting, Lindemann presented a mechanism that provides the foundation for contemplating the pressure dependence of unimolecular reactions. Since that time, our ability to model and predict the kinetics of such reactions has grown in leaps and bounds through the synergy of ever more sophisticated experimental studies with increasingly high level theoretical analyses. This review begins with a brief historical overview of the progress from the Lindemann mechanism to the master equation, which now provides the cornerstone for most theoretical analyses. The current status of ab initio transition state theory based implementations of the master equation is then reviewed, beginning with a discussion of the energy resolved chemical conversion rates, followed by a review of the pressure dependence of the thermal kinetics. The latter discussion focusses on the collisional energy and angular momentum transfer rates as well as the complexities of non-thermal effects and of multiple-well multiple-channel reactions. The synergy with recent state-of-the-art experiments is used to motivate these discussions. Attempts to automate the calculations are also briefly reviewed. Throughout the discussion, we provide our perspective on current understanding and continuing challenges and opportunities. One key challenge relates to the coupling of sequences of reactions, which frequently leads to deviations from the classic presumption of thermal reactants.

Formation of Phosphorus Monoxide (PO) in the Interstellar Medium: Insights from Quantum-chemical and Kinetic Calculations

Abstract In recent years, phosphorus monoxide (PO), an important molecule for prebiotic chemistry, has been detected in star-forming regions and in the comet 67P/Churyumov-Gerasimenko. These studies have revealed that, in the interstellar medium (ISM), PO is systematically the most abundant P-bearing species, with abundances that are about one to three times greater than those derived for phosphorus nitride (PN), the second-most abundant P-containing molecule. The reason why PO is more abundant than PN remains still unclear. Experimental studies with phosphorus in the gas phase are not available, probably because of the difficulties in dealing with its compounds. Therefore, the reactivity of atomic phosphorus needs to be investigated using reliable computational tools. To this end, state-of-the-art quantum-chemical computations have been employed to evaluate accurate reaction rates and branching ratios for the P + OH → PO + H and P + H2O → PO + H2 reactions in the framework of a master equation approach based on ab initio transition state theory. The hypothesis that OH and H2O can be potential oxidizing agents of atomic phosphorus is based on the ubiquitous presence of H2O in the ISM. Its destruction then produces OH, which is another very abundant species. While the reaction of atomic phosphorus in its ground state with water is not a relevant source of PO because of emerged energy barriers, the P + OH reaction represents an important formation route of PO in the ISM. Our kinetic results show that this reaction follows an Arrhenius–Kooij behavior, and thus its rate coefficients (α = 2.28 × 10−10 cm3 molecule−1 s−1, β = 0.16 and γ = 0.37 K) increase by increasing the temperature.

Diastereomers and Low-Temperature Oxidation

Diastereomers have historically been ignored when building kinetic mechanisms for combustion. Low-temperature oxidation kinetics, which continues to gain interest in both combustion and atmospheric communities, may be affected by the inclusion of diastereomers in radical chain-branching pathways. In this work, key intermediates and transition states lacking stereochemical specification in an existing diethyl ether low-temperature oxidation mechanism were replaced with their diastereomeric counterparts. Rate coefficients for reactions involving diastereomers were computed with ab initio transition state theory master equation calculations. The presence of diastereomers increased rate coefficients by factors of 1.2-1.6 across various temperatures and pressures. Ignition delay simulations incorporating these revised rate coefficients indicate that the diastereomers enhanced the overall reactivity of the mechanism by almost 15% and increased the peak ketohydroperoxide concentration by 30% in the negative temperature coefficient region at combustion-relevant pressures. These results provide an illustrative indication of the important role of stereomeric effects in oxidation kinetics.

Advancing chemical kinetic modeling

Chemical Engineering Quantitative prediction of the time evolution of chemical mixtures is the central problem of reactive chemical engineering. This is a challenging task because of the thousands of elementary chemical reactions that must be considered in chemical kinetic modeling. Usually, such models are developed and refined gradually over many years. Using broadband rotational spectroscopy, combined with automated ab initio transition state theory–based master equation calculations and high-level thermochemical parametrization, Zaleski et al. reveal an important role of a variety of radical substitution reactions in the flash pyrolysis of acetone that was previously omitted in the corresponding combustion mechanisms. Their unified combination of modeling, experiment, and theory is a promising approach in the development of comprehensive chemical kinetic models. J. Am. Chem. Soc. 143 , 3124 (2021).

Kinetic Study of Gas-Phase Reactions of Pyruvic Acid with HO2

Gas-phase reactions between pyruvic acid (PA) and HO2 radicals were examined using ab initio quantum chemistry and transition state theory. The rate coefficients were determined over a temperature range of 200-400 K including tunneling contributions. Six potential reaction pathways were identified. The two hydrogen abstraction reactions yielding the H2O2 product were found to have high barriers. The HO2 radical was also found to have a catalytic effect on the intramolecular hydrogen transfer reactions occurring by three distinct routes. These hydrogen-shift reactions are very interesting mechanistically although they are highly endothermic. The only reaction that contributes significantly to the consumption of PA is a multistep pathway involving a peroxy-radical intermediate, PA + HO2 → CH3COOH + OH + CO2. This exothermic process has potential atmospheric relevance because it produces an OH radical as a product. Atmospheric models currently have difficulty predicting accurate OH concentrations for certain atmospheric conditions, such as environments free of NOx and the nocturnal boundary layer. Reactions of this sort, although not necessary with PA, may account for a portion of this deficit. The present study helps settle the issue of the relative roles of reaction and photolysis in consumption of PA in the troposphere.

Determination of rate constants for a thermoneutral H-abstraction reaction: Allylic hydrogen abstraction from 1,5-hexadiene by allyl radical

Thermoneutral H-abstraction reactions, which involve the abstraction by resonantly stabilized radicals from olefins to form other resonantly stabilized radicals, have recently been found to be important in high-temperature combustion. They will shift the distribution of resonantly stabilized radicals and affect the molecular weight growth kinetics, thus changing the prediction for aromatic species. The present work provides the first experimental study on a typical thermoneutral H-abstraction reaction: C3H5-A + 1,5-C6H10 = C3H6 + C6H9-A (R1). A rapid compression machine, together with a fast sampling technique, was used to study the high temperature kinetics of 1,5-hexadiene. Experimental conditions that can be used to derive the rate constant of R1 were first identified by sensitivity analysis of a kinetic model for 1,5-hexadiene combustion. The concentration of propene was found to be highly sensitive to the rate constant of R1 over the temperature range of 893–1007 K at 25 bar. By fitting the measured propene profiles, the rate constant of R1 was deduced under selected conditions. Furthermore, the concentration profiles of propene in 1,5-hexadiene pyrolysis from a flow reactor measurement by Wang et al. (Fuel 208, 779–790, 2017) and oxidation from a jet stirred reactor measurement by Vermeire et al. (Proc. Combust. Inst. 37, 1091–1098, 2019) were also used to derive the rate constant of R1 over wider temperature ranges. The rate coefficient of R1 was further calculated by ab initio transition state theory, with energies obtained at the level of DLPNO-CCSD(T)/aug-cc-pVTZ//B2PLYP/cc-pVTZ. The theoretical predictions were found to be in good agreement with the experimentally derived rate constants. The final rate coefficient determined is: kR1=15.058×T3.425exp(−14492.073/RT)cm3mol−1s−1(500−2000K), with an estimated uncertainty of a factor of 1.5.

Formic acid catalyzed keto‐enol tautomerizations for C2and C3enols: Implications in atmospheric and combustion chemistry

AbstractEnols are important species in atmospheric and combustion chemistry. However, their implications in these environments are not well established due to a lack of accurate rate constants and mechanisms to determine their fate. In this work, we investigate the formic acid catalyzed keto‐enol tautomerizations converting vinyl alcohol, propen‐2‐ol and 1‐propenol into acetaldehyde, acetone and propanal, respectively. High‐level ab initio and multistructural torsional variational transition state theory calculations are performed with small‐curvature tunneling corrections to obtain rate constants in the temperature range 200 K‐3000 K. Tunneling is shown to be pronounced as a consequence of very narrow adiabatic potential energy curves, and indicates a need to revisit previous calculations. We show the implications of the studied reactions on the fate of enols under combustion relevant conditions by detailed kinetic modeling simulations. The yield of vinyl alcohol predicted by our calculated rate constants may be useful to lessen the underestimation of organic acids concentrations in current atmospheric models.

Water nucleation at extreme supersaturation.

We report water cluster formation in the uniform postnozzle flow of a Laval nozzle at low temperatures of 87.0 and 47.5 K and high supersaturations of lnS ∼ 41 and 104, respectively. Cluster size distributions were measured after soft single-photon ionization at 13.8 eV with mass spectrometry. Critical cluster sizes were determined from cluster size distributions recorded as a function of increasing supersaturation, resulting in critical sizes of 6-15 and 1, respectively. Comparison with previous data for propane and toluene reveals a systematic trend in the nucleation behavior, i.e., a change from a steplike increase to a gradual increase of the maximum cluster size with increasing supersaturation. Experimental nucleation rates of 5 · 1015 cm-3 s-1 and 2 · 1015 cm-3 s-1 for lnS ∼ 41 and 104, respectively, were retrieved from cluster size distributions recorded as a function of nucleation time. These lie 2-3 orders of magnitude below the gas kinetic collision limit assuming unit sticking probability, but they agree very well with a recent prediction by a master equation model based on ab initio transition state theory. The experimental observations are consistent with barrierless growth at 47.5 K, but they hint at a more complex nucleation behavior for the measurement at 87.0 K.

Ab Initio, Transition State Theory, and Kinetic Modeling Study of the HO2-Assisted Keto-Enol Tautomerism Propen-2-ol + HO2 ⇔ Acetone + HO2 under Combustion, Atmospheric, and Interstellar Conditions.

Keto-enol tautomerisms are important reactions in gaseous and liquid systems with implications in different chemical environments, but their kinetics have not been widely investigated. These reactions can proceed via a unimolecular process or may be catalyzed by another molecule. This work presents a theoretical study of the HO2-catalyzed tautomerism that converts propen-2-ol into acetone at conditions relevant to combustion, atmospheric and interstellar chemistry. We performed CCSD(T)/aug-cc-pVTZ//M06-2X/cc-pVTZ ab initio and multistructural torsional variational transition state theory calculations to compute the forward and reverse rate constants. These rate constants have not been investigated previously, and modelers approximate the kinetics by comparison to analogue reactions. Two features of the potential energy surface of the studied tautomerism are highlighted. First, the HO2 radical exhibits a pronounced catalytic effect by inducing a double hydrogen atom transfer reaction with a much lower barrier than that of the unimolecular process. Second, a prereactive complex is formed with a strong OH···π hydrogen bond. The role of the studied reaction under combustion conditions has been assessed via chemical kinetic modeling of 2-butanol (a potential alternative fuel) oxidation. The HO2-assisted process was found to not be competitive with the unimolecular and HCOOH-assisted tautomerisms. The rate constants for the formation of the prereactive complex were calculated with the variable reaction coordinate transition state theory, and pressure effects were estimated with the system-specific quantum Rice-Ramsperger-Kassel theory; this allowed us to investigate the role of the complex by using the canonical unified statistical model. The formation and equilibration of the prereactive complex, which is also important at low pressures, enhances the reactivity by inducing a large tunneling effect that leads to a significant increase of the rate constants at cold and ultracold temperatures. These findings may help to understand and model the fate of complex organic molecules in the interstellar medium, and suggest an alternative route for the high energy barrier keto-enol tautomerism which otherwise is not kinetically favored at low temperatures.

Simulating the density of organic species in the atmosphere of Titan with a coupled ion-neutral photochemical model

We present a one-dimensional coupled ion-neutral photochemical kinetics and diffusion model to study the atmospheric composition of Titan in light of new theoretical kinetics calculations and scientific findings from the Cassini–Huygens mission. The model extends from the surface to the exobase. The atmospheric background, boundary conditions, vertical transport and aerosol opacity are all constrained by the Cassini–Huygens observations. The chemical network includes reactions between hydrocarbons, nitrogen and oxygen bearing species. It takes into account neutrals and both positive and negative ions with masses extending up to 116 and 74 u, respectively. We incorporate high-resolution isotopic photoabsorption and photodissociation cross sections for N2 as well as new photodissociation branching ratios for CH4 and C2H2. Ab initio transition state theory calculations are performed in order to estimate the rate coefficients and products for critical reactions.Main reactions of production and loss for neutrals and ions are quantitatively assessed and thoroughly discussed. The vertical distributions of neutrals and ions predicted by the model generally reproduce observational data, suggesting that for the small species most chemical processes in Titan’s atmosphere and ionosphere are adequately described and understood; some differences are highlighted. Notable remaining issues include (i) the total positive ion density (essentially HCNH+) in the upper ionosphere, (ii) the low mass negative ion densities (CN−,C3N−/C4H−) in the upper atmosphere, and (iii) the minor oxygen-bearing species (CO2, H2O) density in the stratosphere. Pathways towards complex molecules and the impact of aerosols (UV shielding, atomic and molecular hydrogen budget, nitriles heterogeneous chemistry and condensation) are evaluated in the model, along with lifetimes and solar cycle variations.

Kinetics of 1-butyl and 2-butyl radical reactions with molecular oxygen: Experiment and theory

The reaction of O2 with butyl radicals is a key early step in the oxidation of n-butane, which is a prototypical alkane fuel with combustion properties that mimic those of many larger alkanes. Current combustion mechanisms employ kinetic descriptions for such radical oxidations that are based on fairly limited information. The present work employs a combination of experiment and theory to probe the kinetics of O2 reacting with both 1- and 2-butyl radicals. The experiments employ laser photolysis to generate butyl radicals and thereby initiate the reaction kinetics. Photoionization mass spectrometric observations of the time-dependent butyl radical concentration yield rate coefficients for the overall reaction. The experiments cover temperatures ranging from 200 to 500 K and He bath gas pressures ranging from 0.3 to 6 Torr. Ab initio transition state theory (TST) based master equation calculations are used to predict the kinetics over a broad range of conditions. The calculations consider both the barrierless R + O2 entrance channel, treated with direct CASPT2 variable reaction coordinate TST, and the decomposition of the RO2 complex to HO2 + alkenes, treated with CCSD(T)/CBS based TST. Theory and experiment are in good agreement, with maximum discrepancies of about 30%, suggesting the appropriateness of the theory based predictions for conditions of greater relevance to combustion. The kinetic description arising from this work should be of considerable utility to combustion modeling of n-butane, as well as of other related saturated hydrocarbons.

Theory and modeling of relevance to prompt-NO formation at high pressure

An improved understanding of NOx formation at high pressures would be of considerable utility to efforts to develop advanced combustion devices. A combination of theoretical and modeling studies are implemented in an effort to improve the accuracy of models for the prompt NO process, which is the dominant source of NO under many conditions, and to improve our understanding of the role of this process at high pressures. The theoretical effort implements state-of-the-art treatments of NCN thermochemistry, the interrelated CH + N2 and NCN + H kinetics, and the kinetics of the NCN + OH reaction. For both reaction systems, we implement high level ab initio transition state theory based master equation simulations paying particular attention to the role of stabilization processes. For the NCN + H kinetics we include a treatment of inter-system crossing. The modeling effort focuses on exploring the role of pressure and prompt NO for premixed laminar flames at pressures ranging from 1 to 15 atm, via a comparison with the available experimental data. Additional simulations at higher pressures further explore the mechanistic changes at the pressures of relevance to applied combustion devices (e.g., 100 atm).

Theoretical kinetic studies for low temperature oxidation of two typical methylcyclohexyl radicals

To improve the understanding of low temperature oxidation of methyl cyclohexane, the potential energy surfaces for O2 addition to two of its radicals (tcy-C6H10(*)CH3 with a tertiary radical site and ortho-cy-C6H10(*)CH3 with a secondary radical site in the ortho position to the methyl substitution) have been investigated by high level quantum chemical calculations. The reaction kinetics was studied by the ab initio transition state theory based on master equation methodology. The relationship between low temperature oxidation reactivity and molecular structures was explored, typically in terms of the barrier heights of 1,5 H-shift for peroxy radicals. The computed phenomenological rate constants reveal that the ROO stabilization dominates the fates of two methyl cyclohexyl radicals reacting with O2 at pressures higher than 1atm over the studied temperature range. The balance between ROO stabilization, HO2 elimination, QOOH stabilization, and OH formation was further revealed by branching ratios of these four types of reactions. This study extends kinetic data for cyclic alkanes oxidation in a wide range of pressure and temperature.

Theoretical investigation of low detection sensitivity for underivatized carbohydrates in ESI and MALDI.

Electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) mainly generate protonated ions from peptides and proteins but sodiated (or potassiated) ions from carbohydrates. The ion intensities of sodiated (or potassiated) carbohydrates generated by ESI and MALDI are generally lower than those of protonated peptides and proteins. Ab initio calculations and transition state theory were used to investigate the reasons for the low detection sensitivity for underivatized carbohydrates. We used glucose and cellobiose as examples and showed that the low detection sensitivity is partly attributable to the following factors. First, glucose exhibits a low proton affinity. Most protons generated by ESI or MALDI attach to water clusters and matrix molecules. Second, protonated glucose and cellobiose can easily undergo dehydration reactions. Third, the sodiation affinities of glucose and cellobiose are small. Some sodiated glucose and cellobiose dissociate into the sodium cations and neutral carbohydrates during ESI or MALDI process. The increase of detection sensitivity of carbohydrates in mass spectrometry by various methods can be rationalized according to these factors. Copyright © 2016 John Wiley & Sons, Ltd.