Neutral Species Research Articles

Trend in the Electron Affinities of Fluorophenyl Radicals ·C6H5-xFx (1 ≤ x ≤ 4).

The electron affinities (EAs) of a series of ·C6H5-xFx (1 ≤ x ≤ 4) fluorophenyl radicals are determined from the photoelectron spectra of their associated fluorophenide anions generated from C6H6-xFx (1 ≤ x ≤ 4) fluorobenzene precursors. The spectra show a near-linear incremental increase in EA of 0.4 eV/x. The spectra exhibit vibrationally unresolved and broad detachment transitions consistent with significant differences in the molecular structures of the anion and neutral radical species. The experimental EAs and broad spectra are consistent with density functional theory calculations on these species. While the anion detachment transitions all involve an electron in a non-bonding orbital, the differences in structure between the neutral and anion are in part due to repulsion between the lone pair on the C-center on which the excess charge is localized and neighboring F atoms. The C6H5-xFx- (2 ≤ x ≤ 4) spectra show features at lower binding energy that appear to be due to constitutional isomers formed in the ion source.

Influence of plasma parameters on low-k SiCOH film grown by plasma-enhanced chemical vapor deposition using dimethyldimethoxysilane

Here, we report the influence of the electron density and the electron temperature on the reduction of dielectric constant in the SiCOH thin film using dimethyldimethoxysilane (DMDMS) as a function of pressure. The measured electron density and electron temperature decreased as increasing the pressure. The decrease in the measured electron density with increasing pressure can be attributed to local electron kinetics. Moreover, the decreasing electron temperature is caused by increased inelastic collisions between electrons and neutral species in the chamber. It is identified that CH3 radicals are less dissociated from DMDMS molecular at higher pressure by a quadrupole mass spectroscopy. As increasing pressure, the increase of the Si–CH3 bonds in SiCOH thin films is confirmed by Fourier transform infrared spectroscopy. As a result, the dielectric constant and refractive index of the SiCOH films are reduced at low electron density and electron temperature.

Modeling the Partitioning of Anionic Carboxylic and Perfluoroalkyl Carboxylic and Sulfonic Acids to Octanol and Membrane Lipid.

Perfluoroalkyl carboxylic and sulfonic acids (PFCAs and PFSAs, respectively) have low acid dissociation constant values and are, therefore, deprotonated under most experimental and environmental conditions. Hence, the anionic species dominate their partitioning between water and organic phases, including octanol and phospholipid bilayers which are often used as model systems for environmental and biological matrices. However, data for solvent-water (SW) and membrane-water partition coefficients of the anion species are only available for a few per- and polyfluoroalkyl substances (PFAS). In the present study, an equation is derived using a Born-Haber cycle that relates the partition coefficients of the anions to those of the corresponding neutral species. It is shown via a thermodynamic analysis that for carboxylic acids (CAs), PFCAs, and PFSAs, the log of the solvent-water partition coefficient of the anion, log KSW (A- ), is linearly related to the log of the solvent-water partition coefficient of the neutral acid, log KSW (HA), with a unity slope and a solvent-dependent but solute-independent intercept within a PFAS (or CA) family. This finding provides a method for estimating the partition coefficients of PFCAs and PFSAs anions using the partition coefficients of the neutral species, which can be reliably predicted using quantum chemical methods. In addition, we have found that the neutral octanol-water partition coefficient, log KOW , is linearly correlated to the neutral membrane-water partition coefficient, log KMW ; therefore, log KOW , being a much easier property to estimate and/or measure, can be used to predict the neutral log KMW . Application of this approach to KOW and KMW for PFCAs and PFSAs demonstrates the utility of this methodology for evaluating reported experimental data and extending anion property data for chain lengths that are unavailable. Environ Toxicol Chem 2023;00:1-12. © 2023 SETAC.

Extended Conductor-like Polarizable Continuum Solvation Model (CPCM-X) for Semiempirical Methods.

We have developed a new method to accurately account for solvation effects in semiempirical quantum mechanics based on a polarizable continuum model (PCM). The extended conductor-like polarizable continuum model (CPCM-X) incorporates a computationally efficient domain decomposition conductor-like screening model (ddCOSMO) for extended tight binding (xTB) methods and uses a post-processing approach based on established solvation models, like the conductor-like screening model for real solvents (COSMO-RS) and the universal solvent model based on solute electron density (SMD). According to various benchmarks, the approach performs well across a broad range of systems and applications, including hydration free energies, non-aqueous solvation free energies, and large supramolecular association reactions of neutral and charged species. Our method for computing solvation free energies is much more accurate than the current methods in the xtb program package. It improves the accuracy of solvation free energies by up to 40% for larger supramolecular association reactions to match even the accuracy of higher-level DFT-based solvation models like COSMO-RS and SMD while being computationally more than 2 orders of magnitude faster. The proposed method and the underlying ddCOSMO model are readily available for a wide variety of solvents and are accessible in xtb for use in various computational applications.

Blue-Emitting 2D- and 3D-Zinc Coordination Polymers Based on Schiff-Base Amino Acid Ligands

The solvothermal reaction of Zn(NO3)2·4H2O, 1-OH-2-naphthaldehyde, and 2-methylalanine (mAla) in MeOH leads to the formation of complex {[ZnL1]}2n (1) (H2L1 = the Schiff-base resulting from the reaction of 1-OH-2-naphthaldehyde and mAla) in good yields. The structure of the neutral species, as determined by single-crystal crystallography, describes a two-dimensional coordination polymer, with repeating {Zn2} units bridged by syn, anti-carboxylate groups of the Schiff-base ligands. Repeating the same reaction using glycine (gly) instead of mAla leads to the formation of complex {[ZnL2]·0.33MeOH}3n (2.0.33MeOH) (H2L2 = the Schiff-base resulting from the reaction of 1-OH-2-naphthaldehyde and gly), again in good yields. Complex 2 describes a three-dimensional coordination polymer based on {Zn2} building blocks, arranged by anti, anti-carboxylate groups in a 3D motif. Complexes 1 and 2 were found to strongly emit at ~435 nm (λexc = 317 nm) both in solution and solid state, with complex 2 displaying a slightly longer lifetime of τav = 2.45 ns vs. τav = 2.02 ns for 1.

Molecular dynamics approach for the calculation of the surface loss probabilities of neutral species in argon–methane plasma

AbstractMolecular dynamics simulations are carried out for calculating the surface loss probabilities of neutral species from an argon–methane plasma. These probabilities are the sum of the sticking and surface recombination probabilities. This study considers both the formation of reactive and nonreactive volatile species for evaluating recombination probabilities. Results show that stable species are reflected when hydrocarbon film starts growing on the surface. CH3 is mainly lost by surface recombination leading to the formation of volatile products while very little contributes to film growth. C2H has surface loss probability in agreement with the literature. While C2H loss is usually attributed to sticking on the surface, our results show that its main loss process is due to surface recombination.

Electron density control in WSe2 monolayers via photochlorination

Modulation of the Fermi level using an ultraviolet (UV)-assisted photochemical method is demonstrated in tungsten diselenide monolayers. Systematic shifts and relative intensities between charged and neutral exciton species indicate a progressive and controllable decrease of the electron density and switch tungsten diselenide from n-type to a p-type semiconductor. The presence of chlorine in the 2D crystal shifts the Fermi level closer to the valence band while the effect can be only partially reversible via continuous wave laser rastering process. Chlorine species in the lattice are validated by x-ray photoelectron spectroscopy, while density functional theory calculations predict that adsorption of chlorine on the selenium vacancy sites leads to p-type doping. The results of our study indicate that photochemical techniques have the potential to enhance the performance of various 2D materials, making them suitable for integrated optoelectronics such as lateral nanopatterned p–n junctions.

Influence of 2-naphthoic acid anchoring groups to the photovoltaic performance of zinc phthalocyanine-based photosensitizers in dye-sensitized solar cell

Two different zinc phthalocyanines bearing different numbers of 2-naphthoic acid anchoring groups at the peripheral positions were synthesized and characterized with UV–Vis, proton nuclear magnetic resonance (1H NMR), fouirer transform infrared (FT-IR), and matrix-assisted laser desorption/ionization mass (MALDI-TOF MS) spectroscopy. Then their electrochemical, and spectroelectrochemical performances were investigated to predict their suitability of them as photosensitizers in dye-sensitized solar cells (DSSC). In the voltammetric analysis results, [2,9,16-Tri-(4-carboxyethylphenoxy)-23-(4-[6-carboxy-2-naphtoxy]) substituted zinc(II) phthalocyanine (ZnPc(3)) and [2,9,16,23-tetra-(4-(6-carboxy-2-naphthoxy) substituted zinc(II) phthalocyanine (ZnPc(4)) illustrate similar electron transfer processes. The substituent environments of the complexes slightly influenced the position and reversibility of the redox couples. Redox processes of ZnPc(3) bearing unsymmetrical carboxyethylphenoxy and 2-naphthoic acid anchoring groups slightly shift towards the positive potentials concerning ZnPc(4) bearing symmetrical 2-naphthoic acid substituents. Peak positions of both complexes reflecting the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) positions indicate the suitability of the complexes for the efficient charge carrier transferring from these photosensitizers to the semiconductor and redox mediator in the DSSC. Pc-based spectroelectrochemical responses of the complexes supported the HOMO and LUMO positions for both neutral and electrogenerated ZnPc species. DSSC responses indicated that ZnPc(3), which has the asymmetric carboxyethylphenoxy and 2-naphthoic acid substituents, gave higher DSSC efficiency withshort-circuit photocurrent density (JSC) (9.54 mA cm−2), open circuit potential (VOC) (697 mV), fill factor (FF) (51%), incident monochromatic photon-to-current conversion efficiency (IPCE) (51%), and power conversion efficiency (ƞ) (3.4%) parameters concerning ZnPc(4) bearing symmetric 2-naphthoic acid anchoring groups.

LiDB: Database of molecular radiative lifetimes for plasma processes

Abstract LiDB is a newly developed database of molecular vibrational and vibronic state radiative lifetimes. It has been created with the aim of enabling radiative effects to be properly captured in low-temperature plasma models. Datasets have been generated for 36 molecules using comprehensive and highly accurate molecular line lists from the ExoMol spectroscopic database. The main data output of LiDB is radiative lifetimes at vibrational state resolution. Partial lifetimes, which give information on the dominant decay channels in a molecule, are also provided. LiDB is freely available to the scientific community and is hosted at www.exomol.com/lidb. Users can dynamically view molecular datasets or use a specially-designed application programming interface to make data requests. LiDB will continue to expand in the future by adding more molecules, important isotopologues, and neutral and singly-charged atomic species.

Mass spectrometry and in situ x-ray photoelectron spectroscopy investigations of organometallic species induced by the etching of germanium, antimony and selenium in a methane-based plasma

Organometallic positive ions were identified in inductively coupled plasmas by means of mass spectrometry during the etching of Ge, Sb, Se materials. A preliminary study was focused on identifying M x H y + (M = Ge, Sb, Se) positive ion clusters during a H2/Ar etching process. The methane addition to the H2/Ar mixture generates CH x reactive neutral species. The latter react with the metalloids within gas phase to form M x C y H z + organometallic ions. In addition, the etching of Sb2Se3 and Ge19.5Sb17.8Se62.7 bulk targets forms mixed products via ion-molecule reactions as evidenced by the presence of SeSbC x H y + ion clusters. Changes in surface composition induced by the newly formed organometallic structures were investigated using in situ x-ray photoelectron spectroscopy. In the case of the Ge and Sb surfaces, (M)–M–C x environments broadened the Ge 2p3/2, Ge 3d, Sb 3d and Sb 4d spectra to higher values of binding energy. For the Se surface, only the hydrogen and methyl bonding could explain the important broadening of the Se 3d core level. It was found that the Ge39Se61 thin film presents an induced (Ge)–Ge–Se entity on the Ge 2p3/2 and Ge 3d core levels.

Colour tunability by optically induced electron transfer in diarylamine-dibenzothiophene derivatives

Three arylamino-dibenzothiophene derivatives (Ary2-DBT, Ary2-DBTSO and Ary2-DBTSO2), based on a molecular architecture D-π-D, have been designed and synthesized. The three compounds, showing different oxidation states of the S-heterocycle (sulfide, sulfoxide and sulfone), have been studied in order to investigate the effects of both the neutral and radical species on the photophysical properties. To this purpose, cyclic voltammetry, UV/Vis-NIR and fluorescence spectroscopy, TDDFT calculation, and EPR spectroscopy measurements were performed. Moreover, spectroelectrochemical measurements have demonstrated the ability of these molecular systems to shift their colour output by following a change in the applied voltage. Finally, as a proof of concept, electrochromic devices have been fabricated to demonstrate the functionality of these dyes as anodic components.

N‐Doped Octagon‐Containing HBC as Redox and pH Chiroptical Switch in the NIR

AbstractThe optical and chiroptical properties of an aza‐HBC‐oct‐[5]helicene have been studied and also modulated by means of protonation or oxidation. In both cases, the generated species shows a new absorption band in the NIR region that is not present in the neutral species. This result enables this N‐doped nanographene to act both as optical and, remarkably, as chiroptical switch since both the CD and CPL can be modulated by external stimuli such as redox or pH changes.

X-ray photodesorption of complex organic molecules in protoplanetary disks

Context. X-rays emitted from pre-main-sequence stars at the center of protoplanetary disks can induce nonthermal desorption from interstellar ices populating the cold regions of the disk. This process, known as X-ray photodesorption, needs to be quantified for complex organic molecules (COMs), including acetonitrile CH3CN, which has been detected in several disks. Aims. The purpose of this work is to experimentally estimate the X-ray photodesorption yields of neutral species from pure CH3CN ices and from interstellar ice analogs for which CH3CN is mixed either in a CO-dominated ice or in a H2O-dominated ice. Methods. The ices, grown in an ultrahigh vacuum chamber, were irradiated at 15 K by soft X-rays from synchrotron light (SOLEIL synchrotron) in the N K edge region (395–420 eV) and in the O K edge region (530–555 eV). X-ray photodesorption was probed in the gas phase via quadrupole mass spectrometry by monitoring the changes in the mass signals due to the X-ray irradiation of the ices. X-ray photodesorption yields were derived from the mass signals and were extrapolated to higher X-ray energies in order to provide astrophysical yields adapted to astrochemical models. Results. X-ray photodesorption of the intact CH3CN is detected from pure CH3CN ices and from mixed 13CO:CH3CN ices, with an experimental yield of about 5 × 10−4 molecules photon−1 at 560 eV. When mixed in H2O-dominated ices, X-ray photodesorption of the intact CH3CN at 560 eV is below its detection limit, which is 10−4 molecules photon−1. Yields associated with the desorption of HCN, CH4, and CH3 are also provided. The derived astrophysical yields significantly depend on the local conditions expected in protoplanetary disks, that is, on the ice composition and on the local X-ray irradiation spectrum. They vary from ~10−4 to ~10−6 molecules photon−1 for the X-ray photodesorption of intact CH3CN from CO-dominated ices. Only upper limits varying from ~5 × 10−5 to ~5 × 10−7 molecules photon−1 could be derived for the X-ray photodesorption of intact CH3CN from H2O-dominated ices. Conclusions. X-ray photodesorption of intact CH3CN from interstellar ices might in part explain the abundances of CH3CN observed in protoplanetary disks. The desorption efficiency is expected to vary with the local physical conditions, hence with the disk region considered.

Non-equilibrium modeling on the aerothermodynamic characteristics of hypersonic inflatable reentry vehicle

In this study a 2D two-temperature chemical non-equilibrium model is established to investigate the flow characteristics and chemical reactions processes around hypersonic inflatable reentry vehicle at different flight altitudes and reentry velocities. This chemical kinetic model is based on the Gupta model and modified by comparing the species mole fractions at thermal equilibrium condition with the results obtained by Saha equation. In order to validate the model, the calculations are performed for a blunt cone ELECTRE and a cylinder, the predicted heat flux and pressure are compared with experimentally measured data and the maximum differences on heat flux and wall pressure are less than 20% and 5%, respectively. Then the flow characteristics behind the shock wave and wall heat flux are discussed in detail for Titans vehicle. It is found that the pressure declines with the increase of altitude and reentry velocity, this variation trend is opposite to the wall heat flux, whose maximum value increases from 58 kw/m2 to 107 kw/m2 with the rise of flight altitude from 79 to 88 km due to the large temperature and component gradients. This indicates that the aerodynamic force and heat flux should be taken into account simultaneously for the design of inflatable reentry vehicle. By analyzing the chemical reactions processes behind the strong shock wave, it is seen that not only the dissociation reactions of N2 and O2 molecules play an important role, but also the neutral species exchange reactions contribute to the density change of species. The dominant ionization reactions are N+O→NO++e and NO+M→4NO++e+M4, while the ionization processes are weak, and the maximum ionization degree is smaller than 1%. The analysis of dominant chemical reactions can provide a reference for the numerical modeling study of hypersonic reentry vehicle.

Hydrogeological conditions and hydrogeochemistry of the Kamenskoye hydro-radon occurrence, Novosibirsk, Russia

Hydrogeological and hydrogeochemical conditions, the concentrations of major and some minor ions and 222Rn were determined in the Kamenskoye hydro-radon occurrence in the Southern part of West Siberia. Two different aquifer systems were revealed in the hydrogeological section: the Quaternary sediments with pore waters and the Upper Paleozoic granites including the waters of regional fracturing zone and fracture-vein waters. They are located in a common mixing area and are affected by flooding and anthropogenic pollution. Mineral radon fracture-vein waters in granites, not affected by anthropogenic impact, have been revealed in two boreholes. These waters are cool, fresh (TDS 613.4 to 689.9 mg/L) and Si4+ content within a range from 10.3 to 13.6 mg/L. The pH of these waters is neutral to weakly alkaline (6.9–7.8), the gases dissolved in the waters are oxygen and nitrogen. The determined activity of 222Rn varies within the range from 1101 to 1570 Bq/L; 238U concentration varies between 5.6·10−3–6.5·10−3 mg/L, while 226Ra ranges from 2.7·10−9 to 1.8·10−8 mg/L. The relative fractions of cations (Mg2+, Ca2+, Na+, Sr2+, Ba2+) decrease with an increase in TDS value due to the formation of poorly soluble carbonate and sulphate compounds. The forms of Fe(II) are represented by Fe2+, FeHCO3+, FeCO30, and Fe(III) migrates in the forms of hydroxo complexes Fe(OH)2+ and neutral species Fe(OH)30. Manganese migrates mainly as a cation, while other forms (MnHCO3+, MnCO30) are less abundant, and MnSO40, MnCl+, MnOH+ are minor. The chemical forms of nickel and copper migration are free cations, as well as hydrocarbonate and carbonate complexes. Copper, as well as beryllium, also migrate as hydroxo complexes. The forms in which chemical elements migrate and their migration coefficients provide evidence that the equilibrium minerals become more complicated when passing from surface waters (greenalite, siderite, and ferrihydrite and greenalite) to the fracture-vein waters in the Upper Paleozoic granites saturated with dolomite, calcite, talc, magnesite and rhodochrosite.

Twisted Diindeno‐Fused Dibenzo[a,h]anthracene Derivatives and their Dianions

AbstractWe report a facile synthesis of diindeno‐fused dibenzo[a,h]anthracene derivatives (DIDBA‐2Cl, DIDBA‐2Ph, and DIDBA‐2H) with different degrees of non‐planarity using three substituents (chloro, phenyl, and hydrogen) of various sizes. The planarization of their cores, as evidenced by the decreased end‐to‐end torsional angles, was confirmed by X‐ray crystallography. Their enhanced energy gaps with twisting were investigated by a combination of spectroscopic and electrochemical methods with density functional theory, which showed a transition from singlet open‐shell to closed‐shell configuration. Moreover, their doubly reduced states, DIDBA‐2Ph2− and DIDBA‐2H2−, were achieved by chemical reduction. The structures of dianions were identified by X‐ray crystallographic analysis, which elucidated that the electron charging further distorted the backbones. The electronic structure of the dianions was demonstrated by experimental and theoretical approaches, suggesting decreased energy gaps with larger non‐planarity, different from the neutral species.

Twisted Diindeno-Fused Dibenzo[a,h]anthracene Derivatives and their Dianions.

We report a facile synthesis of diindeno-fused dibenzo[a,h]anthracene derivatives (DIDBA-2Cl, DIDBA-2Ph, and DIDBA-2H) with different degrees of non-planarity using three substituents (chloro, phenyl, and hydrogen) of varying sizes. The planarization of their cores, as evidenced by the decreased end-to-end torsional angles, was confirmed by X-ray crystallography. Their enhanced energy gaps with twisting were investigated by a combination of spectroscopic and electrochemical methods with density functional theory, resulting in a transition from singlet open-shell to closed-shell configuration. Moreover, their doubly-reduced states, DIDBA-2Ph2- and DIDBA-2H2-, were achieved by chemical reduction. The structures of dianions were identified by X-ray crystallographic analysis, elucidating that the electron charging further distorted the backbones. The electronic structure of the dianions was demonstrated by experimental and theoretical approaches, suggesting decreased energy gaps with larger non-planarity, different from the neutral species.

Towards understanding of stepwise acid-base dissociation in systems inclined to tautomerism: Nitro derivatives of fluorescein in dimethyl sulfoxide

Understanding the dissociation of polyprotic acids in solution is important for many branches of chemistry and related sciences. A most important and at the same time knotty problem is the relation between the values of the stepwise dissociation constants. Sometimes even in a series of compounds that belong to the same family, the ratio of these constants varies in a wide range. This paper is aimed at disclosing the (unusual) relations between the first and second dissociation constants of the nitro derivatives of fluorescein in dimethyl sulfoxide. Some of the compounds were synthesized for the first time and characterized. The thermodynamic pKa values for 8 dyes were determined using the spectrophotometric method in buffer solutions and compared with the data for 12 earlier examined compounds; the Ka1/Ka2 ratio varies within an extremely wide range of 0.2 to 4 × 107. It is demonstrated that the peculiarities of the tautomerism of molecules, single-, and double-charged anions play a decisive role in this case. Neutral species, H2R, are represented by the quinonoid and lactonic tautomers. The fraction of the latter is higher for all the dyes with the free carboxylic group. For the single-charged anions, HR–, of the 4′- and 5′-mononitrofluoresceins, i.e., dyes with the NO2 group in the phthalic acid residue, the carboxylic group is dissociated (COO–) while the OH group not. In contrast, for the dyes bearing the NO2 group in the 4,5-; 4,5,4′-; 4,5,5′-; or 2,4,5,7-positions the HR– ions exist mainly as a tautomer with the dissociated hydroxyl group (O–) and un-dissociated COOH group. To the dianions, R2–, of fluorescein dyes a structure with the COO– and O– groups is normally ascribed. However, for the 4,5-dinitro-2,7-dibromofluorescein in DMSO, the fraction of the dianion existing as a lactonic tautomer is substantial; previously, it was shown that this tautomer of the R2– ion predominates for the 2,4,5,7-tetranitrofluorescein, 2,4,5,7,4′-, and 2,4,5,7,5′-pentanitrofluoresceins. After assessing the tautomeric relationships and singling out the so-called microscopic constants, the order of dissociating functional groups and the influence of the substituents in the xanthenes moiety became easy to understand. The values for the microscopic dissociation constants were confirmed by the pKa s of the model compounds with blocked carboxylic groups, COOCH3 or COOC2H5.

A Boltzmann Electron Drift Diffusion Model for Atmospheric Pressure Non-Thermal Plasma Simulations

We introduce a fluid computational model for the numerical simulation of atmospheric pressure dielectric barrier discharge plasmas. Ion and neutral species are treated with an explicit drift diffusion approach. The Boltzmann relation is used to compute the spatial distribution of electrons as a function of the electrostatic potential and the ionic charge density. This technique, widely used to speed up particle and fluid models for low-pressure conditions, poses several numerical challenges for high-pressure conditions and large electric field values typical of applications involving atmospheric-pressure plasmas. We develop a robust algorithm to solve the non-linear electrostatic Poisson problem arising from the Boltzmann electron approach under AC electric fields based on a charge-conserving iterative computation of the reference electric potential and electron density. We simulate a volumetric reactor in dry air, comparing the results yielded by the proposed method with those obtained when the drift diffusion approach is used for all charged species, including electrons. We show that the proposed methodology retains most of the physical information provided by the reference modeling approach while granting a substantial advantage in terms of computation time.

Binding mechanism of disulfide species to ferric hemeproteins: The case of metmyoglobin

The interactions of the heme iron of hemeproteins with sulfide and disulfide compounds are of potential interest as physiological signaling processes. While the interaction with hydrogen sulfide has been described computationally and experimentally, the reaction with disulfide, and specifically the molecular mechanism for ligand binding has not been studied in detail. In this work, we study the association process for disulfane and its conjugate base disulfanide at different pH conditions. Additionally, by means of advanced sampling techniques based on multiple steered molecular dynamics, we provide free energy profiles for ligand migration for both acid/base species, showing a similar behavior to the previously reported for the related H2S/HS¯ pair. Finally, we studied the ligand interchange reaction (H2O/H2S, HS¯ and H2O/HSSH, HSS¯) by means of hybrid quantum mechanics-molecular mechanics calculations. We show that the anionic species are able to displace more efficiently the H2O bound to the iron, and that the H-bond network in the distal cavity can help the neutral species to perform the reaction. Altogether, we provide a molecular explanation for the experimental information and show that the global association process depends on a fine balance between the migration towards the active site and the ligand interchange reaction.