Ab Initio Thermochemistry Research Articles

In situ mass spectrometric investigation to probe GeSn growth dynamics and mechanisms in the chemical vapor deposition processes

GeSn has attracted increasing attention due to its tunable bandgap from indirect to direct resulting in unique electronic and optoelectronic capabilities. Chemical vapor deposition (CVD) is well acknowledged as an advanced growth method for GeSn, demonstrating its capability with grown materials for infrared lasers and detector development. As an in situ diagnostics of the CVD process, a residual gas analyzer (RGA) could enable the detection of all gaseous species during growth, thus probing the growth dynamics and mechanism. Therefore, it is highly desirable but is lacking in the (Si)GeSn research community. This work utilized an RGA equipped with a specialized differential vacuum pumping system to analyze the mass spectra of the GeSn CVD precursors of SnCl4, GeH4, and their combination. The spectra of SnCl4 collected from gas samples at a standard base pressure of 0.3 Torr display consistent fragments with central mass-to-charge ratios (m/z) of 78, 120, 155, 225, and 260, corresponding to Sn+, SnCl2+, SnCl+, SnCl2+, SnCl3+, and SnCl4+, respectively. These profiles closely resemble those observed in the National Institute of Standards and Technology and Wiley and Matsumoto et al. The simultaneous introduction of SnCl4 and GeH4 at a combined pressure of several tens of Torr yields spectra, indicating a chemical reaction that produces GeCl4 at room temperature in the vacuum chamber and tubing. Utilizing Gaussian16 and ORCA codes, the ab initio and density functional thermochemistry computations were employed to predict potential essential reactions and validate the experimental findings.

W4Λ: Leveraging Λ Coupled-Cluster for Accurate Computational Thermochemistry Approaches.

High-accuracy composite wave function methods like Weizmann-4 (W4) theory, high-accuracy extrapolated ab initio thermochemistry (HEAT), and the Feller-Peterson-Dixon (FPD) approach enable sub-kJ/mol accuracy in gas-phase thermochemical properties. Their biggest computational bottleneck is the evaluation of the valence post-CCSD(T) correction term. We demonstrate here, for the W4-17 thermochemistry benchmark and subsets thereof, that the Λ coupled-cluster expansion converges more rapidly and smoothly than the regular coupled-cluster series. By means of CCSDT(Q)Λ and CCSDTQ(5)Λ, we can considerably (up to an order of magnitude) accelerate W4- and W4.3-type calculations without loss in accuracy, leading to the W4Λ and W4.3Λ computational thermochemistry protocols.

Unraveling the electronic structure of LuH, LuN, and LuNH: building blocks of new materials.

Advances in superconductor technology have been pursued for decades, moving towards room temperature models, such as a postulated nitrogen-doped lutetium hydride network. While experimental observations have been contradictory, insight into the building blocks of potential new superconductor materials can be gained theoretically, unravelling the fascinating electronic structure of these compounds at a molecular level. Here, the fundamental building blocks of lutetium materials (LuH, LuN, and LuNH) have been examined. The structures, spectroscopic constants for the ground and excited states, and the potential energy curves have been obtained for these species using complete active self-consistent field (CASSCF) and multireference configuration interaction with Davidson's correction (MRCI+Q) methods. For LuNH, the energetic properties of its isomers are determined. The bond dissociation energies of the three building blocks are calculated with the state-of-the-art f-block ab initio correlation consistent composite approach (f-ccCA) and the high accuracy extrapolated ab initio thermochemistry (HEAT) scheme. As well, an analysis of different formation pathways of LuNH has been provided.

Accurate ab initio thermochemistry of the Groups 10–12 difluorides, dichlorides, oxides and sulfides

Literature-available experimental and theoretical total atomization energies and enthalpies of formation (at 0 and 298 K) of the Groups 10–12 transition metal difluorides, dichlorides, oxides and sulfides are systematically compared with their CCSD(T)/CBS counterparts calculated in the present study. The species, for which the best agreement between various experimental and/or theoretical values was found, NiF2, NiCl2, NiO, NiS, CuF2, CuO, CuS, ZnF2, ZnCl2, ZnO, ZnS, PdCl2, PdO, AgO, AgS, CdF2, CdCl2 are recommended to be used as reference compounds in the reaction-based approaches to predict gas-phase thermochemical properties of the larger transition metal complexes. Additional experimental measurements are suggested for CuCl2, ZnS, PdF2, AgF2, AgCl2, CdO, CdS, PdS exhibiting the largest discrepancies in their earlier reported thermochemical characteristics and/or with our theoretical predictions.

Detailed kinetic mechanism of polyoxymethylene dimethyl ether 3 (PODE3). Part I: Ab initio thermochemistry and kinetic predictions for key reactions

In recent years, polyoxymethylene dimethyl ether 3 (PODE3) has emerged as a promising fuel additive to mitigate soot emissions in diesel engines, garnering significant research attention. Several detailed kinetic mechanisms of PODE3 have been developed to investigate its reaction pathways and to simulate its combustion process. Typically, these mechanisms employ analogy methods based on rate constants derived primarily from PODE1 sub-mechanisms. However, in this study, we present, for the first time, high-level ab initio quantum chemical calculations directly on PODE3 itself. (1) The bond dissociation energies (BDEs) of all CH and CO bonds in dimethyl ether (DME) and PODEn (n = 1–5) were calculated using combined compound methods (CBS-APNO/G3/G4). (2) The obtained BDE results were then utilized to investigate the unimolecular decomposition reactions of PODE3, demonstrating good agreement with previous Molecular Dynamics simulation results. (3) The rate constants of hydrogen abstraction reactions of PODE3 by H˙,C˙H3,CH3O˙,O˙H,HO˙2,O2 were calculated with all possible pre-reaction or post-reaction complexes identified. The rate constants of the H-atom abstraction reactions were found to primarily depend on the energy barriers following the order: O˙H>CH3O˙>H˙>C˙H3>HO˙2>O2. However, the abstraction by H˙ can dominate as temperature increases. (4) The rate constants of β-scission and isomerization reactions of PODE3 radicals were also computed. The calculated β-scission reaction rates supported the suitability of the rate analogy for PODEn, employing the long-chain PODE3. The energy barriers of the isomerization reactions with long chain transition states were comparable to the energy barrier of the β-scission reactions and are much lower than that in the case of PODE1 radicals. (5) The thermochemistry properties of all involved species, including PODE4–5 and their radicals, were calculated with the combined compound methods (CBS-APNO/G3/G4) for further combustion modeling. Considering PODE3′s nature as a long-chain PODEn, the rate constants computed for PODE3 can serve as a solid foundation for developing detailed mechanisms for PODE4–5.

CKineticsDB─An Extensible and FAIR Data Management Framework and Datahub for Multiscale Modeling in Heterogeneous Catalysis.

A great advantage of computational research is its reproducibility and reusability. However, an enormous amount of computational research data in heterogeneous catalysis is barricaded due to logistical limitations. Sufficient provenance and characterization of data and computational environment, with uniform organization and easy accessibility, can allow the development of software tools for integration across the multiscale modeling workflow. Here, we develop the Chemical Kinetics Database, CKineticsDB, a state-of-the-art datahub for multiscale modeling, designed to be compliant with the FAIR guiding principles for scientific data management. CKineticsDB utilizes a MongoDB back-end for extensibility and adaptation to varying data formats, with a referencing-based data model to reduce redundancy in storage. We have developed a Python software program for data processing operations and with built-in features to extract data for common applications. CKineticsDB evaluates the incoming data for quality and uniformity, retains curated information from simulations, enables accurate regeneration of publication results, optimizes storage, and allows the selective retrieval of files based on domain-relevant catalyst and simulation parameters. CKineticsDB provides data from multiple scales of theory (ab initio calculations, thermochemistry, and microkinetic models) to accelerate the development of new reaction pathways, kinetic analysis of reaction mechanisms, and catalysis discovery, along with several data-driven applications.

Linking Experimental and Ab Initio Thermochemistry of Adsorbates with a Generalized Thermochemical Hierarchy.

Enthalpies of formation of adsorbates are crucial parameters in the microkinetic modeling of heterogeneously catalyzed reactions since they quantify the stability of intermediates on the catalyst surface. This quantity is often computed using density functional theory (DFT), as more accurate methods are computationally still too expensive, which means that the derived enthalpies have a large uncertainty. In this study, we propose a new error cancellation method to compute the enthalpies of formation of adsorbates from DFT more accurately through a generalized connectivity-based hierarchy. The enthalpy of formation is determined through a hypothetical reaction that preserves atomistic and bonding environments. The method is applied to a data set of 60 adsorbates on Pt(111) with up to 4 heavy (non-hydrogen) atoms. Enthalpies of formation of the fragments required for the bond balancing reactions are based on experimental heats of adsorption for Pt(111). The comparison of enthalpies of formation derived from different DFT functionals using the isodesmic reactions shows that the effect of the functional is significantly reduced due to the error cancellation. Thus, the proposed methodology creates an interconnected thermochemical network of adsorbates that combines experimental with ab initio thermochemistry in a single and more accurate thermophysical database.

Sub 20 cm-1 computational prediction of the CH bond energy - a case of systematic error in computational thermochemistry.

The bond dissociation energy of methylidyne, D0(CH), is studied using an improved version of the High-Accuracy Extrapolated ab initio Thermochemistry (HEAT) approach as well as the Feller-Peterson-Dixon (FPD) model chemistry. These calculations, which include basis sets up to nonuple (aug-cc-pCV9Z) quality, are expected to be capable of providing results substantially more accurate than the ca. 1 kJ mol-1 level that is characteristic of standard high-accuracy protocols for computational thermochemistry. The calculated 0 K CH bond energy (27 954 ± 15 cm-1 for HEAT and 27 956 ± 15 cm-1 for FPD), along with equivalent treatments of the CH ionization energy and the CH+ dissociation energy (85 829 ± 15 cm-1 and 32 946 ± 15 cm-1, respectively), were compared to the existing benchmarks from Active Thermochemical Tables (ATcT), uncovering an unexpected difference for D0(CH). This has prompted a detailed reexamination of the provenance of the corresponding ATcT benchmark, allowing the discovery and subsequent correction of a systematic error present in several published high-level calculations, ultimately yielding an amended ATcT benchmark for D0(CH). Finally, the current theoretical results were added to the ATcT Thermochemical Network, producing refined ATcT estimates of 27 957.3 ± 6.0 cm-1 for D0(CH), 32 946.7 ± 0.6 cm-1 for D0(CH+), and 85 831.0 ± 6.0 cm-1 for IE(CH).

Evaluating the Atmospheric Loss of H2 by NO3 Radicals: A Theoretical Study

Molecular hydrogen (H2) is now considered among the most prominent substitute for fossil fuels. The environmental impacts of a hydrogen economy have received more attention in the last years, but still, the knowledge is relatively poor. In this work, the reaction of H2 with NO3 radical (the dominant night-time detergent of the atmosphere) is studied for the first time using high-level composite G3B3 and modification of high accuracy extrapolated ab initio thermochemistry (mHEAT) methods in combination with statistical kinetics analysis using non-separable semi-classical transition state theory (SCTST). The reaction mechanism is characterized, and it is found to proceed as a direct H-abstraction process to yield HNO3 plus H atom. The reaction enthalpy is calculated to be 12.8 kJ mol−1, in excellent agreement with a benchmark active thermochemical tables (ATcT) value of 12.2 ± 0.3 kJ mol−1. The energy barrier of the title reaction was calculated to be 74.6 and 76.7 kJ mol−1 with G3B3 and mHEAT methods, respectively. The kinetics calculations with the non-separable SCTST theory give a modified-Arrhenius expression of k(T) = 10−15 × T0.7 × exp(−6120/T) (cm3 s−1) for T = 200–400 K and provide an upper limit value of 10−22 cm3 s−1 at 298 K for the reaction rate coefficient. Therefore, as compared to the main consumption pathway of H2 by OH radicals, the title reaction plays an unimportant role in H2 loss in the Earth’s atmosphere and is a negligible source of HNO3.

Elaborated thermochemical treatment of HF, CO, N2, and H2O: Insight into HEAT and its extensions.

Empirical, highly accurate non-relativistic electronic total atomization energies (eTAEs) are established by combining experimental or computationally converged treatments of the nuclear motion and relativistic contributions with the total atomization energies of HF, CO, N2, and H2O obtained from the Active Thermochemical Tables. These eTAEs, which have estimated (2σ) uncertainties of less than 10 cm-1 (0.12 kJ mol-1), form the basis for an analysis of high-level ab initio quantum chemical calculations that aim at reproducing these eTAEs for the title molecules. The results are then employed to analyze the performance of the high-accuracy extrapolated ab initio thermochemistry, or High-Accuracy Extrapolated Ab Initio Thermochemistry (HEAT), family of theoretical methods. The method known as HEAT-345(Q), in particular, is found to benefit from fortuitous error cancellation between its treatment of the zero-pointenergy, extrapolation errors in the Hartree-Fock and coupled cluster contributions, neglect of post-(T) core-correlation, and the basis-set error involved in higher-level correlation corrections. In addition to shedding light on a longstanding curiosity of the HEAT protocol-where the cheapest HEAT-345(Q) performs comparably to the theoretically more complete HEAT-456QP procedure-this study lays the foundation for extended HEAT variants that offer substantial improvements in accuracy relative to the established approaches.

Ab initio thermochemistry study of polymorphism in the Si2N2(NH) analog of Si2N2O

We present a systematic density functional theory (DFT) study of the structural, bonding and electronic properties of the Si2N2(NH) polymorphs. This recently synthesized compound is a direct analog of Si2N2O in which the oxygen is replaced by an NH group. We show that a local-density approximation (LDA) description in the static lattice approximation gives a good account of the lowest energy orthorhombic phase of both the parent oxide and imide analog. In this work we extend our systematic comparisons between Si2N2O and Si2N2(NH) to denser tetragonal and monoclinic polymorphs. For Si2N2(NH) we find that the tetragonal and monoclinic polymorphs have energies 0.8 and 1.8 eV higher than (respectively) that of the orthorhombic ground state, similar to their Si2N2O counterparts (0.6 and 1.4 eV, respectively). We elucidate differences in chemical binding in Si2N2O and Si2N2(NH) polymorphs using Bader charge analysis and conclude that the imide systems possess slightly less ionic character than their oxide counterpart. Using the modified Becke-Johnson (MBJ) meta-LDA approach we find that orthorhombic Si2N2O and Si2N2NH have direct gaps of 5.65 and 5.75 eV, respectively, in excellent agreement with experiment. Relative to the orthorhombic Si2N2O (5.65 eV, direct), the band gaps in the denser polymorphs increase and become indirect (tetragonal: 5.72 eV, monoclinic: 6.06 eV). We find more complex trends in Si2N2NH in which the band gaps are also indirect in character, but decrease to 3.91 eV in the tetragonal phase, and then increase to 4.18 eV (Γ → D) in the monoclinic case.

Density Functional Geometries and Zero-Point Energies in Ab Initio Thermochemical Treatments of Compounds with First-Row Atoms (H, C, N, O, F).

Density functionals are often used in ab initio thermochemistry to provide optimized geometries for single-point evaluations at a high level and to supply estimates of anharmonic zero-point energies (ZPEs). Their use is motivated by relatively high accuracy at a modest computational expense, but a thorough assessment of geometry-related error seems to be lacking. We have benchmarked 53 density functionals, focusing on approximations of the first four rungs and on relatively small basis sets for computational efficiency. Optimized geometries of 279 neutral first-row molecules (H, C, N, O, F) are judged by energy penalties relative to the best available geometries, using the composite model ATOMIC/B5 as energy probe. Only hybrid functionals provide good accuracy with root-mean-square errors around 0.1 kcal/mol and maximum errors below 1.0 kcal/mol, but not all of them do. Conspicuously, first-generation hybrids with few or no empirical parameters tend to perform better than highly parameterized ones. A number of them show good accuracy already with small basis sets (6-31G(d), 6-311G(d)). As is standard practice, anharmonic ZPEs are estimated from scaled harmonic values. Statistics of the latter show less performance variation among functionals than observed for geometry-related error, but they also indicate that ZPE error will generally dominate. We have selected PBE0-D3/6-311G(d) for the next version of the ATOMIC protocol (ATOMIC-2) and studied it in more detail. Empirical expressions have been calibrated to estimate bias corrections and 95% uncertainty intervals for both geometry-related error and scaled ZPEs.

Valence Photoionization and Energetics of Vanillin, a Sustainable Feedstock Candidate.

We studied the valence photoionization of vanillin by photoelectron photoion coincidence spectroscopy in the 8.20-19.80 eV photon energy range. Vertical ionization energies by EOM-IP-CCSD calculations reproduce the photoelectron spectral features. Composite method calculations and Franck-Condon simulation of the weak, ground-state band yield the adiabatic ionization energy of the most stable vanillin conformer as 8.306(20) eV. The lowest energy dissociative photoionization channels correspond to hydrogen atom, carbon monoxide, and methyl losses, which form the dominant C8H7O3+ (m/z 151) and the less intense C7H8O2+ (m/z 124) and C7H5O3+ (m/z 137) fragment ions in parallel dissociation channels at modeled 0 K appearance energies of 10.13(1), 10.40(3), and 10.58(10) eV, respectively. On the basis of the breakdown diagram, we explore the energetics of sequential methyl and carbon monoxide loss channels, which dominate the fragmentation mechanism at higher photon energies. The 0 K appearance energy for sequential CO loss from the m/z 151 fragment to C7H7O2+ (m/z 123) is 12.99(10) eV, and for sequential CH3 loss from the m/z 123 fragment to C6H4O2+ (m/z 108), it is 15.40(20) eV based on the model. Finally, we review the thermochemistry of the bi- and trifunctionalized benzene derivatives guaiacol, hydroxybenzaldehyde, anisaldehyde, and vanillin. On the basis of isodesmic functional group exchange reactions, we propose new enthalpies of formations, among them ΔfH°298K(vanillin, g) = -383.5 ± 2.9 kJ mol-1. These mechanistic insights and ab initio thermochemistry results will support analytical works to study lignin conversion involving vanillin.

Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

AbstractPreviously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high‐accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero‐ and infinite‐pressure limits; (c) a hindered‐rotor model for HOCO that implicitly includes the cis‐ and trans‐conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.

High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency.

A number of economical modifications to the high-accuracy extrapolated ab initio thermochemistry (HEAT) model chemistry are evaluated. The two resulting schemes, designated as mHEAT and mHEAT+, are designed for efficient and pragmatic evaluation of molecular energies in systems somewhat larger than can be practically studied by the unapproximated HEAT scheme. It is found that mHEAT+ produces heats of formation with nearly subchemical (±1 kJ/mol) accuracy at a substantially reduced cost relative to the full scheme. Total atomization energies calculated using the new thermochemical recipes are compared to the results of the HEAT-345(Q) model chemistry, and enthalpies of formation for the three protocols are also compared to Active Thermochemical Tables. Finally, a small selection of transition states is studied using mHEAT and mHEAT+, which illuminates some interesting features of reaction barriers and serves as an initial benchmark of the performance of these model chemistries for chemical kinetics applications.

Ring-polymer molecular dynamics studies of thermal rate coefficients for reaction F + H2O → HF + OH

The prototype tetra-atomic reaction F + H2O → HF + OH plays a significant role in both atmospheric and astronomical chemistry. In this work, thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics (RPMD) method on a full-dimensional potential energy surface (PES). This PES is the most accurate one for the title reaction, as demonstrated by the correct barrier height and reaction energy, compared to the benchmark calculations by the focal point analysis and the high accuracy extrapolated ab initio thermochemistry methods. The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation technique, and some experimental measurements. As has been found in many RPMD applications, quantum effects, including tunneling and zero-point energy effects, can be efficiently and effectively captured by the RPMD method. In addition, the convergence of the results with respect to the number of beads is rapid, which is also consistent with previous RPMD applications.

A master equation simulation for the •OH + CH3OH reaction.

A combined (fixed-J) two-dimensional master-equation/semi-classical transition state theory/variational Rice-Ramsperger-Kassel-Marcus approach has been used to compute reaction rate coefficients of •OH with CH3OH over a wide range of temperatures (10-2500 K) and pressures (10-1-104 Torr) based on a potential energy surface that has been constructed using a modification of the high accuracy extrapolated ab initio thermochemistry (HEAT) protocol. The calculated results show that the title reaction is nearly pressure-independent when T > 250 K but depends strongly on pressure at lower temperatures. In addition, the preferred mechanism and rate constants are found to be very sensitive to temperature. The reaction pathway CH3OH + •OH → CH3O• + H2O proceeds exclusively through tunneling at exceedingly low temperatures (T ≤ 50 K), typical of those established in interstellar environments. In this regime, the rate constant is found to increase with decreasing temperature, which agrees with low-temperature experimental results. The thermodynamically favored reaction pathway CH3OH + •OH → •CH2OH + H2O becomes dominant at higher temperatures (T ≥ 200 K), such as those found in Earth's atmosphere as well as combustion environments. By adjusting the ab initio barrier heights slightly, experimental rate constants from 200 to 1250 K can be satisfactorily reproduced.

Ab initio thermal rate coefficients for H + NH3 ⇌ H2 + NH2

AbstractThe reversible reaction NH3 + H ⇌ H2 + NH2, which plays an important role in NH3 fuel combustion, is studied with a theoretical approach that combines the high‐accuracy extrapolated ab initio thermochemistry (HEAT) protocol with semiclassical transition state theory (SCTST). The calculated forward reaction is endothermic by 11.8 ± 1 kJ/mol, in nearly perfect agreement with the active thermochemical tables (ATcT) value of 11.5 ± 0.2 kJ/mol. Using this improved thermochemistry yields better rate constants, especially at low temperatures. Experimental rate constants available from 400 to 2000 K for the forward and reverse reaction pathways can be reproduced (within 20%) by the calculations from first principles.

Bethe-Salpeter correlation energies of atoms and molecules.

A variety of approaches are presented for the computation of atomic and molecular correlation energies based on the Bethe-Salpeter equation in the framework of the adiabatic-connection fluctuation-dissipation theorem. The performance of the approaches is assessed by computing the total energies of the atoms H-Ne and the atomization energies of the high-accuracy extrapolated ab initio thermochemistry set of small molecules as well as by determining the bond lengths and harmonic vibrational frequencies of the metal monoxides MO with M=Ca-Zn.

High-accuracy extrapolated ab initio thermochemistry of the NCN radical

Enthalpies of formation of the cyanonitrene radical, NCN, were calculated according to the HEAT (High-accuracy Extrapolated Ab initio Thermochemistry) protocol. The obtained, recommended values are 451.7 ± 1.0 kJ mol−1 and 452.2 ± 1.0 kJ mol−1 at 0 K and 298.15 K, respectively (gas phase, 1 bar). The calculated values are in agreement with the most recent Active Thermochemical Tables analysis and some of the previous experimental and computational results. The uncertainties associated with the HEAT values are, however, considerably smaller.