Templating Bicarbonate in the Second Coordination Sphere Enhances Electrochemical CO2 Reduction Catalyzed by Iron Porphyrins.

Bicarbonate-based electrolytes are ubiquitous in aqueous electrochemical CO2 reduction, particularly in heterogenous catalysis, where they demonstrate improved catalytic performance relative to other buffers. In contrast, the presence of bicarbonate in organic electrolytes and its roles in homogeneous electrocatalysis remain underexplored. Here, we investigate the influence of bicarbonate on iron porphyrin-catalyzed electrochemical CO2 reduction. We show that bicarbonate is a viable proton donor in organic electrolyte (pKa = 20.8 in dimethyl sulfoxide) and that urea pendants in the second coordination sphere can be used to template bicarbonate in the vicinity of a molecular iron porphyrin catalyst. The templated binding of bicarbonate increases its acidity, resulting in a 1500-fold enhancement in catalytic rates relative to unmodified parent iron porphyrin. This work emphasizes the importance of bicarbonate speciation in wet organic electrolytes and establishes second-sphere bicarbonate templating as a design strategy to harness this adventitious acid and enhance CO2 reduction catalysis.

Deciphering Distinct Overpotential-Dependent Pathways for Electrochemical CO2 Reduction Catalyzed by an Iron-Terpyridine Complex.

[Fe(tpyPY2Me)]2+ ([Fe]2+) is a homogeneous electrocatalyst for converting CO2 into CO featuring low overpotentials of <100 mV, near-unity selectivity, and high activity with turnover frequencies faster than 100 000 s-1. To identify the origins of its exceptional performance and inform future catalyst design, we report a combined computational and experimental study that establishes two distinct mechanistic pathways for electrochemical CO2 reduction catalyzed by [Fe]2+ as a function of applied overpotential. Electrochemical data shows the formation of two catalytic regimes at low (ηTOF/2 of 160 mV) and high (ηTOF/2 of 590 mV) overpotential plateaus. We propose that at low overpotentials [Fe]2+ undergoes a two-electron reduction, two-proton-transfer mechanism (electrochemical-electrochemical-chemical-chemical, EECC), where turnover occurs through the dicationic iron complex, [Fe]2+. Computational analysis supports the importance of the singlet ground-state electronic structure for CO2 binding and that the rate-limiting step is the second protonation in this low-overpotential regime. When more negative potentials are applied, an additional electron-transfer event occurs through either a stepwise or proton-coupled electron-transfer (PCET) pathway, enabling catalytic turnover from the monocationic iron complex ([Fe]+) via an electrochemical-chemical-electrochemical-chemical (ECEC) mechanism. Comparison of experimental kinetic data obtained from variable controlled potential electrolysis (CPE) experiments with direct product detection with calculated rates obtained from the energetic span model supports the PCET pathway as the most likely mechanism. Moreover, we build upon this mechanistic understanding to propose the design of an improved ligand framework that is predicted to stabilize the key transition states identified in our study and explore their electronic structures using an energy decomposition analysis. Taken together, this work highlights the value of synergistic computational/experimental approaches to decipher mechanisms of new electrocatalysts and direct the rational design of improved platforms.

Oxygen Isotope Exchange between Carbon Dioxide and Iron Oxides on Mars' Surface.

An investigation of the fundamental processes leading to the incorporation of 18O isotopes in carbon dioxide and in iron oxides is critical to understanding the atmospheric evolution and geochemistry of Mars. Whereas signatures of 18O have been observed by the Phoenix Lander and the sample analysis at Mars for carbon dioxide, the underlying isotopic exchange pathways with minerals of the crust of Mars are still elusive. Here, we reveal that reactions of gaseous 18O-carbon dioxide over goethite (FeO(OH)) and hematite (Fe2O3) lead to an 18O transfer from the atmosphere that enriches the 18O content of the iron oxides in the absence of water and light. This proof-of-concept study shows that isotopic enrichment processes on Mars not only are limited to the atmosphere but also proceed via chemical interaction with dry iron oxides. These processes are decisive to comprehending the 18O cycle between the atmosphere and the surface on the planetary scale.

Exploring the Limits of Second- and Third-Order Møller-Plesset Perturbation Theories for Noncovalent Interactions: Revisiting MP2.5 and Assessing the Importance of Regularization and Reference Orbitals.

This work systematically assesses the influence of reference orbitals, regularization, and scaling on the performance of second- and third-order Møller-Plesset perturbation theory wave function methods for noncovalent interactions (NCIs). Testing on 19 data sets (A24, DS14, HB15, HSG, S22, X40, HW30, NC15, S66, AlkBind12, CO2Nitrogen16, HB49, Ionic43, TA13, XB18, Bauza30, CT20, XB51, and Orel26rad) covers a wide range of different NCIs including hydrogen bonding, dispersion, and halogen bonding. Inclusion of potential energy surfaces from different hydrogen bonds and dispersion-bound complexes gauges accuracy for nonequilibrium geometries. Fifteen methods are tested. In notation where nonstandard choices of orbitals are denoted as methods:orbitals, these are MP2, κ-MP2, SCS-MP2, OOMP2, κ-OOMP2, MP3, MP2.5, MP3:OOMP2, MP2.5:OOMP2, MP3:κ-OOMP2, MP2.5:κ-OOMP2, κ-MP3:κ-OOMP2, κ-MP2.5:κ-OOMP2, MP3:ωB97X-V, and MP2.5:ωB97X-V. Furthermore, we compare these methods to the ωB97M-V and B3LYP-D3 density functionals, as well as CCSD. We find that the κ-regularization (κ = 1.45 au was used throughout) improves the energetics in almost all data sets for both MP2 (in 17 out of 19 data sets) and OOMP2 (16 out of 19). The improvement is significant (e.g., the root-mean-square deviation (RMSD) for the S66 data set is 0.29 kcal/mol for κ-OOMP2 versus 0.67 kcal/mol for MP2) and for interactions between stable closed-shell molecules, not strongly dependent on the reference orbitals. Scaled MP3 (with a factor of 0.5) using κ-OOMP2 reference orbitals (MP2.5:κ-OOMP2) provides significantly more accurate results for NCIs across all data sets with noniterative O(N6) scaling (S66 data set RMSD: 0.10 kcal/mol). Across the entire data set of 356 points, the improvement over standard MP2.5 is approximately a factor of 2: RMSD for MP3:κ-OOMP2 is 0.25 vs 0.50 kcal/mol for MP2.5. The use of high-quality density functional reference orbitals (ωB97X-V) also significantly improves the results of MP2.5 for NCI over a Hartree-Fock orbital reference. All our assessments and conclusions are based on the use of the medium-sized aug-cc-pVTZ basis to yield results that are directly compared against complete basis set limit reference values.

Controlled Single-Electron Transfer via Metal-Ligand Cooperativity Drives Divergent Nickel-Electrocatalyzed Radical Pathways.

Electrocatalysis enables the construction of C-C bonds under mild conditions via controlled formation of carbon-centered radicals. For sequences initiated by alkyl halide reduction, coordinatively unsaturated Ni complexes commonly serve as single-electron transfer agents, giving rise to the foundational question of whether outer- or inner-sphere electron transfer oxidative addition prevails in redox mediation. Indeed, rational design of electrochemical processes requires the discrimination of these two electron transfer pathways, as they can have outsized effects on the rate of substrate bond activation and thus impact radical generation rates and downstream product selectivities. We present results from combined synthetic, electroanalytical, and computational studies that examine the mechanistic differences of single electron transfer to alkyl halides imparted by Ni metal-ligand cooperativity. Electrogenerated reduced Ni species, stabilized by delocalized spin density onto a redox-active tpyPY2Me polypyridyl ligand, activates alkyl iodides via outer-sphere electron transfer, allowing for the selective activation of alkyl iodide substrates over halogen atom donors and the controlled generation and sequestration of electrogenerated radicals. In contrast, the Ni complex possessing a redox-innocent pentapyridine congener activates the substrates in an inner-sphere fashion owning to a purely metal-localized spin, thereby activating both substrates and halogen atom donors in an indiscriminate fashion, generating a high concentration of radicals and leading to unproductive dimerization. Our data establish that controlled electron transfer via Ni-ligand cooperativity can be used to limit undesired radical recombination products and promote selective radical processes in electrochemical environments, providing a generalizable framework for designing redox mediators with distinct rate and potential requirements.

Metal-Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO2 Reduction at Low Overpotentials.

Biological and heterogeneous catalysts for the electrochemical CO2 reduction reaction (CO2RR) often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over the hydrogen evolution reaction (HER). Here, we report a molecular iron(II) system that captures this design concept in a homogeneous setting through the use of a redox non-innocent terpyridine-based pentapyridine ligand (tpyPY2Me). As a result of strong metal-ligand exchange coupling between the Fe(II) center and ligand, [Fe(tpyPY2Me)]2+ exhibits redox behavior at potentials 640 mV more positive than the isostructural [Zn(tpyPY2Me)]2+ analog containing the redox-inactive Zn(II) ion. This shift in redox potential is attributed to the requirement for both an open-shell metal ion and a redox non-innocent ligand. The metal-ligand cooperativity in [Fe(tpyPY2Me)]2+ drives the electrochemical reduction of CO2 to CO at low overpotentials with high selectivity for CO2RR (>90%) and turnover frequencies of 100 000 s-1 with no degradation over 20 h. The decrease in the thermodynamic barrier engendered by this coupling also enables homogeneous CO2 reduction catalysis in water without compromising selectivity or rates. Synthesis of the two-electron reduction product, [Fe(tpyPY2Me)]0, and characterization by X-ray crystallography, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), variable temperature NMR, and density functional theory (DFT) calculations, support assignment of an open-shell singlet electronic structure that maintains a formal Fe(II) oxidation state with a doubly reduced ligand system. This work provides a starting point for the design of systems that exploit metal-ligand cooperativity for electrocatalysis where the electrochemical potential of redox non-innocent ligands can be tuned through secondary metal-dependent interactions.

The Ground State Electronic Energy of Benzene.

We report on the findings of a blind challenge devoted to determining the frozen-core, full configuration interaction (FCI) ground-state energy of the benzene molecule in a standard correlation-consistent basis set of double-ζ quality. As a broad international endeavor, our suite of wave function-based correlation methods collectively represents a diverse view of the high-accuracy repertoire offered by modern electronic structure theory. In our assessment, the evaluated high-level methods are all found to qualitatively agree on a final correlation energy, with most methods yielding an estimate of the FCI value around -863 mEH. However, we find the root-mean-square deviation of the energies from the studied methods to be considerable (1.3 mEH), which in light of the acclaimed performance of each of the methods for smaller molecular systems clearly displays the challenges faced in extending reliable, near-exact correlation methods to larger systems. While the discrepancies exposed by our study thus emphasize the fact that the current state-of-the-art approaches leave room for improvement, we still expect the present assessment to provide a valuable community resource for benchmark and calibration purposes going forward.

Predicting Excitation Energies of Twisted Intramolecular Charge-Transfer States with the Time-Dependent Density Functional Theory: Comparison with Experimental Measurements in the Gas Phase and Solvents Ranging from Hexanes to Acetonitrile.

Electronically excited states characterized by intramolecular charge transfer play an essential role in many biological processes and optical devices. The ability to make quantitative ab initio predictions of the relative energetics involved is a challenging yet desirable goal, especially for large molecules in solution. In this work, we present a data set of 61 experimental measurements of absorption and emission processes, both in the gas phase and in solvents representing a broad range of polarities, which involve intramolecular charge transfer mediated by a nonzero, "twisted" dihedral angle between one or more donor and acceptor subunits. Among a variety of density functionals investigated within the framework of linear-response theory, the "optimally tuned" LRC-ωPBE functional, which utilizes a system-specific yet nonempirical procedure to specify the range-separation parameter, emerges as the preferred choice. For the entire set of excitation energies, involving changes in dipole moment ranging from 4 to >20 Debye, the mean signed and absolute errors are 0.02 and 0.18 eV, respectively (compared, e.g., to -0.30 and 0.30 for PBE0, 0.44 and 0.47 for LRC-ωPBEh, 0.83 and 0.83 for ωB97X-V). We analyze the performance of polarizable continuum solvation models available in Q-Chem that partition the solvent response into fast and slow time scales, and clear trends emerge when measurements corresponding to the four small 4-(dimethylamino)benzonitrile (DMABN)-like molecules and a charged species are excluded. We make the case that the large errors found only for small molecules in the gas phase and weak solvents cannot be expected to improve via the optimal tuning procedure, which enforces a condition that is exact only in the well-separated donor-acceptor limit, and present empirical evidence implicating the outsized importance for small donor-acceptor systems of relaxation effects that cannot be accounted for by the linear-response time-dependent density functional theory within the adiabatic approximation. Finally, we demonstrate the utility of the optimally tuned density functional approach by targeting the charge-transfer states of a large biomimetic model system for light-harvesting structures in Photosystem II.

Computational Study of an Iron(II) Polypyridine Electrocatalyst for CO2 Reduction: Key Roles for Intramolecular Interactions in CO2 Binding and Proton Transfer.

A solar-driven conversion of CO2 into fuels by artificial photosynthesis would not only mitigate the greenhouse effect but also provide an alternative to obtain fuels in a renewable fashion. To this end, the new iron polypyridine catalyst [Fe(bpyNHEtPY2Me)L2]2+ (L = H2O, CH3CN) was recently developed for the electrochemical reduction of CO2 to CO. In this study, we performed density functional theory (DFT) electronic structure calculations to shed light on a possible pathway for CO2 reduction and the origin of the selectivity between CO2 reduction versus the hydrogen evolution reaction. The metal center remains Lewis acidic throughout the reduction process due to ligand loss and mainly ligand-based reduction stabilized by antiferromagnetic coupling to a high-spin Fe(II) center. This results in a high barrier for hydride formation but a facile addition and activation of CO2 via an η2 coordination and stabilizing hydrogen bonding by the amine group. The second unoccupied equatorial coordination site opens up the possibility for an intramolecular protonation with a coordinated water ligand. This facilitates protonation because not only CO2 but also the proton source H2O is activated and properly aligned for a proton transfer due to the Fe-OH2 bond; consequently, both protonation steps are facile. The moderate ligand field allows a rapid ligand exchange for a second intramolecular protonation step and facilitates an exergonic CO release. The lower selectivity of the related [Fe(bpyOHPY2Me)L2]2+ complex can be related to its more acidic second coordination sphere, which enables an intramolecular proton transfer that is kinetically competitive with CO2 addition.

Energy Decomposition Analysis for Interactions of Radicals: Theory and Implementation at the MP2 Level with Application to Hydration of Halogenated Benzene Cations and Complexes between CO2-· and Pyridine and Imidazole.

To study intermolecular interactions involving radicals at the correlated level, the energy decomposition analysis scheme for second-order MoÌ·ller-Plesset perturbation theory based on absolutely localized molecular orbitals (ALMO-MP2-EDA) is generalized to unrestricted and restricted open-shell MP2. The benefit of restricted open-shell MP2 is that it can provide accurate binding energies for radical complexes where density functional theory can be error-prone due to delocalization errors. As a model application, the open-shell ALMO-MP2-EDA is applied to study the first solvation step of halogenated benzene radical cations, where both halogen- and hydrogen-bonded isomers are possible. We determine that the lighter halogens favor the hydrogen-bonded form, while the iodine-substituted species prefers halogen bonding due to larger polarizability and charge transfer at the halogen. As a second application, relevant to the activation of CO2 in photoelectrocatalysis, complexes of CO2-· interacting with both pyridine and imidazole are analyzed with ALMO-MP2-EDA. The results reveal the importance of charge transfer into the π* orbital of the heterocycle in controlling the stability of the carbamate binding mode, which is favored for pyridine but not for imidazole.

Gas phase formation of c-SiC3 molecules in the circumstellar envelope of carbon stars.

Complex organosilicon molecules are ubiquitous in the circumstellar envelope of the asymptotic giant branch (AGB) star IRC+10216, but their formation mechanisms have remained largely elusive until now. These processes are of fundamental importance in initiating a chain of chemical reactions leading eventually to the formation of organosilicon molecules-among them key precursors to silicon carbide grains-in the circumstellar shell contributing critically to the galactic carbon and silicon budgets with up to 80% of the ejected materials infused into the interstellar medium. Here we demonstrate via a combined experimental, computational, and modeling study that distinct chemistries in the inner and outer envelope of a carbon star can lead to the synthesis of circumstellar silicon tricarbide (c-SiC3) as observed in the circumstellar envelope of IRC+10216. Bimolecular reactions of electronically excited silicon atoms (Si(1D)) with allene (H2CCCH2) and methylacetylene (CH3CCH) initiate the formation of SiC3H2 molecules in the inner envelope. Driven by the stellar wind to the outer envelope, subsequent photodissociation of the SiC3H2 parent operates the synthesis of the c-SiC3 daughter species via dehydrogenation. The facile route to silicon tricarbide via a single neutral-neutral reaction to a hydrogenated parent molecule followed by photochemical processing of this transient to a bare silicon-carbon molecule presents evidence for a shift in currently accepted views of the circumstellar organosilicon chemistry, and provides an explanation for the previously elusive origin of circumstellar organosilicon molecules that can be synthesized in carbon-rich, circumstellar environments.

Two single-reference approaches to singlet biradicaloid problems: Complex, restricted orbitals and approximate spin-projection combined with regularized orbital-optimized Møller-Plesset perturbation theory.

We present a comprehensive study of two single-reference approaches to singlet biradicaloids. These two approaches are based on the recently developed regularized orbital-optimized Møller-Plesset method (κ-OOMP2). The first approach is to combine Yamaguchi's approximate projection (AP) scheme and κ-OOMP2 with unrestricted (U) orbitals (κ-UOOMP2). By capturing only essential symmetry breaking, κ-UOOMP2 can serve as a suitable basis for AP. The second approach is κ-OOMP2 with complex, restricted (cR) orbitals (κ-cROOMP2). Although its applicability is more limited due to the comparative rarity of cR solutions, κ-cROOMP2 offers a simple framework for describing singlet biradicaloids with complex polarization while removing artificial spatial symmetry breaking. We compare the scope of these two methods with numerical studies. We show that AP+κ-UOOMP2 and κ-cROOMP2 can perform similarly well in the TS12 set, a dataset that includes 12 data points for triplet-singlet gaps of several atoms and diatomic molecules with a triplet ground state. This was also found to be true for the barrier height of a reaction involving attack on a cysteine ion by a singlet oxygen molecule. However, we also demonstrate that in highly symmetric systems like C30 (D5h), κ-cROOMP2 is more suitable as it conserves spatial symmetry. Finally, we present an organic biradicaloid that does not have a κ-cROOMP2 solution in which case only AP+κ-UOOMP2 is applicable. We recommend κ-cROOMP2 whenever complex polarization is essential and AP+κ-UOOMP2 for biradicaloids without essential complex polarization but with essential spin-polarization.

Independent amplitude approximations in coupled cluster valence bond theory: Incorporation of 3-electron-pair correlation and application to spin frustration in the low-lying excited states of a ferredoxin-type tetrametallic iron-sulfur cluster.

Coupled cluster valence bond (CCVB) is a simple electronic structure method based on a perfect pairing (PP) reference with 2-pair recouplings for strong electron correlation problems. CCVB is spin-pure, size-consistent, and can exactly (in its active space) separate any molecule into atoms for which unrestricted Hartree-Fock (UHF) at dissociation is the sum of the ground state UHF energies of the atoms. However CCVB is far from a complete description of strong correlations. Its first failure to exactly describe spin-recouplings arises at the level of 3 electron pairs, such as the recoupling of 3 triplet oxygen atoms in the dissociation of singlet ozone. Such situations are often associated with spin frustration. To address this limitation, an extension of CCVB, termed CCVB+i3, is reported here that includes an independent (i) amplitude approximation to the 3-pair recouplings. CCVB+i3 thereby has the same basic computational requirements as those of CCVB, which has previously been shown to be an efficient method. CCVB+i3 correctly separates molecules that CCVB cannot. As a by-product, an independent 2-pair amplitude approximation to CCVB, called PP+i2, is also defined. Remarkably, PP+i2 can also correctly separate systems that CCVB cannot. CCVB+i3 is validated on the symmetric dissociation of D3h ozone. CCVB+i3 is then used to explore the role of 3-pair recouplings in an [Fe4S4(SCH3)4]2- cluster that has been used to model the iron-sulfur core of [Fe4S4] ferredoxins. Using localized PP orbitals, such recouplings are demonstrated to be large in some low-lying singlet excited states of the cluster. Significant 3 pair recoupling amplitudes include the usual triangular motif associated with spin frustration and other geometric arrangements of the 3 entangled pairs across the 4 iron centers.

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation.

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C2H2) n+, just like ionized acetylene clusters. The fragmentation products result from reactive ion-molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C4H4+ and C6H6+ structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C2H2)n+ isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C6H6+ isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.

Probing Ionic Complexes of Ethylene and Acetylene with Vacuum-Ultraviolet Radiation.

Mixed complexes of acetylene-ethylene are studied using vacuum-ultraviolet (VUV) photoionization mass spectrometry and theoretical calculations. These complexes are produced and ionized at different distances from the exit of a continuous nozzle followed by reflectron time-of-flight mass spectrometry detection. Acetylene, with a higher ionization energy (11.4 eV) than ethylene (10.6 eV), allows for tuning the VUV energy and initializing reactions either from a C2H2(+) or a C2H4(+) cation. Pure acetylene and ethylene expansions are separately carried out to compare, contrast, and hence identify products from the mixed expansion: these are C3H3(+) (m/z = 39), C4H5(+) (m/z = 53), and C5H5(+) (m/z = 65). Intensity distributions of C2H2, C2H4, their dimers and reactions products are plotted as a function of ionization distance. These distributions suggest that association mechanisms play a crucial role in product formation closer to the nozzle. Photoionization efficiency (PIE) curves of the mixed complexes demonstrate rising edges closer to both ethylene and acetylene ionization energies. We use density functional theory (ωB97X-V/aug-cc-pVTZ) to study the structures of the neutral and ionized dimers, calculate their adiabatic and vertical ionization energies, as well as the energetics of different isomers on the potential energy surface (PES). Upon ionization, vibrationally excited clusters can use the extra energy to access different isomers on the PES. At farther ionization distances from the nozzle, where the number densities are lower, unimolecular decay is expected to be the dominant mechanism. We discuss the possible decay pathways from the different isomers on the PES and examine the ones that are energetically accessible.

What Is the Structure of the Naphthalene-Benzene Heterodimer Radical Cation? Binding Energy, Charge Delocalization, and Unexpected Charge-Transfer Interaction in Stacked Dimer and Trimer Radical Cations.

The binding energy of the naphthalene(+•)(benzene) heterodimer cation has been determined to be 7.9 ± 1 kcal/mol for C10H8(+•)(C6H6) and 8.1 ± 1 kcal/mol for C10H8(+•)(C6D6) by equilibrium thermochemical measurements using the mass-selected drift cell technique. A second benzene molecule binds to the C10H8(+•)(C6D6) dimer with essentially the same energy (8.4 ± 1 kcal/mol), suggesting that the two benzene molecules are stacked on opposite sides of the naphthalene cation in the (C6D6)C10H8(+•)(C6D6) heterotrimer. The lowest-energy isomers of the C10H8(+•)(C6D6) and (C6D6)C10H8(+•)(C6D6) dimer and trimer calculated using the M11/cc-pVTZ method have parallel stacked structures with enthalpies of binding (-ΔH°) of 8.4 and 9.0 kcal/mol, respectively, in excellent agreement with the experimental values. The stacked face-to-face class of isomers is calculated to have substantial charge-transfer stabilization of about 45% of the total interaction energy despite the large difference between the ionization energies of benzene and naphthalene. Similarly, significant delocalization of the positive charge is found among all three fragments of the (C6D6)C10H8(+•)(C6D6) heterotrimer, thus leaving only 46% of the total charge on the central naphthalene moiety. This unexpectedly high charge-transfer component results in activating two benzene molecules in the naphthalene(+•)(benzene)2 heterotrimer cation to associate with a third benzene molecule at 219 K to form a benzene trimer cation and a neutral naphthalene molecule. The global minimum of the C10H8(+•)(C6H6)2 heterotrimer is found to be the one where the naphthalene cation is sandwiched between two benzene molecules. It is remarkable, and rather unusual, that the binding energy of the second benzene molecule is essentially the same as that of the first. This is attributed to the enhanced charge-transfer interaction in the stacked trimer radical cation.

Assessing electronic structure approaches for gas-ligand interactions in metal-organic frameworks: the CO2-benzene complex.

Adsorption of gas molecules in metal-organic frameworks is governed by many factors, the most dominant of which are the interaction of the gas with open metal sites, and the interaction of the gas with the ligands. Herein, we examine the latter class of interaction in the context of CO2 binding to benzene. We begin by clarifying the geometry of the CO2-benzene complex. We then generate a benchmark binding curve using a coupled-cluster approach with single, double, and perturbative triple excitations [CCSD(T)] at the complete basis set (CBS) limit. Against this ΔCCSD(T)/CBS standard, we evaluate a plethora of electronic structure approximations: Hartree-Fock, second-order Møller-Plesset perturbation theory (MP2) with the resolution-of-the-identity approximation, attenuated MP2, and a number of density functionals with and without different empirical and nonempirical van der Waals corrections. We find that finite-basis MP2 significantly overbinds the complex. On the other hand, even the simplest empirical correction to standard density functionals is sufficient to bring the binding energies to well within 1 kJ/mol of the benchmark, corresponding to an error of less than 10%; PBE-D in particular performs well. Methods that explicitly include nonlocal correlation kernels, such as VV10, vdW-DF2, and ωB97X-V, perform with similar accuracy for this system, as do ωB97X and M06-L.

Relative energies, structures, vibrational frequencies, and electronic spectra of pyrylium cation, an oxygen-containing carbocyclic ring isoelectronic with benzene, and its isomers.

We have studied relative energies, structures, rotational, vibrational, and electronic spectra of the pyrylium cation, an oxygen-containing six-membered carbocyclic ring, and its six isomers, using ab initio quantum chemical methods. Isoelectronic with benzene, the pyrylium cation has a benzenoid structure and is the global minimum on the singlet potential energy surface of C5H5O(+). The second lowest energy isomer, the furfuryl cation, has a five membered backbone akin to a sugar, and is only 16 kcal mol(-1) above the global minimum computed using coupled cluster theory with singles, doubles, and perturbative triple excitations (CCSD(T)) with the correlation consistent cc-pVTZ basis set. Other isomers are 25, 26, 37, 60, and 65 kcal mol(-1) above the global minimum, respectively, at the same level of theory. Lower level methods such as density functional theory (B3LYP) and second order Møller-Plesset perturbation theory performed well when tested against the CCSD(T) results. The pyrylium and furfuryl cations, although separated by only 16 kcal mol(-1), are not easily interconverted, as multiple bonds must be broken and formed, and the existence of more than one transition state is likely. Additionally, we have also investigated the asymptotes for the barrierless ion-molecule association of molecules known to exist in the interstellar medium that may lead to formation of the pyrylium cation.

Attenuated second-order Møller-Plesset perturbation theory: performance within the aug-cc-pVTZ basis.

Attenuated second-order Møller-Plesset perturbation theory (MP2) within the finite aug-cc-pVTZ (aTZ) basis set is developed for inter- and intra-molecular non-bonded interactions. A single attenuation parameter is optimized on the S66 database of 66 intermolecular interactions, leading to a very large RMS error reduction by a factor of greater than 5 relative to standard MP2/aTZ. Attenuation introduces an error of opposite sign to basis set superposition error (BSSE) and overestimation of dispersion interactions in finite basis MP2. A variety of tests including the S22 set, conformer energies of peptides, alkanes, sugars, sulfate-water clusters, and the coronene dimer establish the transferability of the MP2(terfc, aTZ) model to other inter and intra-molecular interactions. Direct comparisons against attenuation in the smaller aug-cc-pVDZ basis shows that MP2(terfc, aTZ) often significantly outperforms MP2(terfc, aDZ), although at higher computational cost. MP2(terfc, aDZ) and MP2(terfc, aTZ) often out-perform MP2 at the complete basis set limit. Comparison of the two attenuated MP2 models against each other and against attenuation using non-augmented basis sets gives insight into the error cancellation responsible for their remarkable success.

Association mechanisms of unsaturated C2 hydrocarbons with their cations: acetylene and ethylene.

The ion-molecule association mechanism of acetylene and ethylene with their cations is investigated by ab initio quantum chemical methods to understand the structures, association energies, and the vibrational and electronic spectra of the products. Stable puckered cyclic isomers are found as the result of first forming less stable linear and bridge isomers. The puckered cyclic complexes are calculated to be strongly bound, by 87, 35 and 56 kcal mol(-1) for acetylene-acetylene cation, ethylene-ethylene cation and acetylene-ethylene cation, respectively. These stable complexes may be intermediates that participate in further association reactions. There are no association barriers, and no significant inter-conversion barriers, so the initial linear and bridge encounter complexes are unlikely to be observable. However, the energy gap between the bridged and cyclic puckered isomers greatly differs from complex to complex: it is 44 kcal mol(-1) in C(4)H(4)(+), but only 6 kcal mol(-1) in C(4)H(8)(+). The accurate CCSD(T) calculations summarized above are also compared against less computationally expensive MP2 and density functional theory (DFT) calculations for structures, relative energies, and vibrational spectra. Calculated vibrational spectra are compared against available experiments for cyclobutadiene cation. Electronic spectra are also calculated using time-dependent DFT.