High-level Electronic Structure Calculations Research Articles

Energetic and Electronic Properties of UO0/± and UF0/±.

High-level electronic structure calculations were conducted to examine the bonding and spectroscopic properties of the UO0/± and UF0/± diatomic molecules. The low-lying Ω states were described by using multireference SO-CASPT2 calculations. The adiabatic electronic affinity (AEA), adiabatic ionization energy (IE), and bond dissociation energy (BDE) were calculated at the Feller-Peterson-Dixon (FPD) level. The ground state of UO is predicted to be 5I4, and that of UF is 4I9/2. The calculated AEAs of UO and UF are 1.123 and 0.453 eV, respectively, and the corresponding IEs are 5.976 and 6.278 eV. The BDE of UO (749.5 kJ/mol) is predicted to be considerably higher than that of UF (627.2 kJ/mol), and both are higher than those predicted for UB, UC, and UN. NBO calculations show strong ionic character for the ground states of UO and UF and bond orders that range from 2 to 3 and from 1 to 2, respectively. Comparisons of the calculated properties to those of the series comprising UB, UC, and UN diatomic molecules are given.

Reaction dynamics of S(3P) with 1,3-butadiene and isoprene: crossed-beam scattering, low-temperature flow experiments, and high-level electronic structure calculations.

Sulfur atoms serve as key players in diverse chemical processes, from astrochemistry at very low temperature to combustion at high temperature. Building upon our prior findings, showing cyclization to thiophenes following the reaction of ground-state sulfur atoms with dienes, we here extend this investigation to include many additional reaction products, guided by detailed theoretical predictions. The outcomes highlight the complex formation of products during intersystem crossing (ISC) to the singlet surfaces. Here, we employed crossed-beam velocity map imaging and high-level ab initio methods to explore the reaction of S(3P) with 1,3-butadiene and isoprene under single-collision conditions and in low-temperature flows. For the butadiene reaction, our experimental results show the formation of thiophene via H2 loss, a 2H-thiophenyl radical through H loss, and thioketene through ethene loss at a slightly higher collision energy compared to previous observations. Complementary Chirped-Pulse Fourier-Transform mmWave spectroscopy (CP-FTmmW) measurements in a uniform flow confirmed the formation of thioketene in the reaction at 20 K. For the isoprene reaction, we observed analogous products along with the 2H-thiophenyl radical arising from methyl loss and C3H4S (loss of ethene or H2 + acetylene). CP-FTmmW detected the formation of thioformaldehyde via loss of 1,3-butadiene, again in the 20 K flow. Coupled-cluster calculations on the pathways found by the automated kinetic workflow code KinBot support these findings and indicate ISC to the singlet surface, leading to the generation of various long-lived intermediates, including 5-membered heterocycles.

Spectroscopy of triatomic [Si, P, O] molecules

Phosphorus is an element essential to sustaining life, and its compounds are widely involved in the biogeochemical cycles on Earth. Although a handful of phosphorus-bearing species, e.g. PO, have thus far been detected in diatomic form in circumstellar envelopes, their formation processes are still poorly understood. In this study, we examine the structure and spectroscopy of the [Si, O, P] system. Based on high-level ab initio electronic structure calculations with the MRCI + Q and CCSD(T) methods, four isomers could be formed and the most stable form predicted to be bent at all theoretical levels. The doublet and quartet potential energy surfaces (PESs) of P(2D)/P(4S) + SiO(1Σ) reactions are explored, and the spectroscopic parameters of the key isomers involved in the reaction are calculated. The present study highlights the possibility of PO formation via photodissociation of bent-SiOP. The results are expected to aid in the spectroscopic detection of these triatomic phosphorous-bearing species and provide insights into similar reactions of isoelectronic systems.

A different view on the deactivation process of 3-hydroxy-salicylidene-methylamine system

Schiff bases stand out as a highly significant class of photochromic materials with widespread applications. The exploration of their photochromic mechanisms has garnered substantial interest over the past decades. In this work, we investigated the photochromic mechanism of 3-hydroxy-salicylidene methylamine (3-OH-SMA) by high-level electronic structure calculations and on-the-fly excited state dynamics simulations. Our investigation revealed the identification of three minimum energy conical intersections between S1 and S0 states, while only the one characterized by the central C = N bond twisting motion was involved in the deactivation process. This finding contrasts with previous reports, suggesting that the excited state intramolecular proton transfer (ESIPT) process was the main reaction channel in 3-OH-SMA. The proposed new decay mechanism provides valuable theoretical insights, paving the way for the further enhancement or rational design of photochromic materials.

Theoretical Kinetic Study on Hydrogen Abstraction Reactions from n-Pentane by NO2.

The interaction of fuel with NOx chemistry is important for the construction of the reaction mechanism and engine application. In this work, the reaction pathways of nC5H12 + NO2 were studied by high-level electronic structure calculations (DLPNO-CCSD(T)-F12/cc-pVTZ-F12//B2PLYPD3/cc-pVTZ). The rate constants were calculated by using the multistructural canonical transition-state theory with the Eckart tunneling method (TST/MS-T/ET). The studied condition is in a wide temperature range of 298-2400 K. The influence of MS-T anharmonicity and tunneling effect will be clarified for these site-specific H-abstraction pathways. The result reflects the large deviation introduced by the treatment of MS-T anharmonicity, especially at a high temperature. For the same type of reactions, the rate constants of H-abstraction both occurring at the secondary carbon are not almost identical. The branching ratios show that abstraction from the secondary site forming cis-HONO (R2c) contributes 36-78% to nC5H12 consumption in the temperature range of 298-2400 K. The current results show that the multistructural torsional anharmonicity has a crucial influence on the accurate estimation of branching ratios.

Accurate Calculation of Many-Body Energies in Water Clusters Using a Classical Geometry-Dependent Induction Model.

We incorporate geometry-dependent distributed multipole and polarizability surfaces into an induction model that is used to describe the 3- and 4-body terms of the interaction between water molecules. The moment expansion is carried out up to the hexadecapole with the multipoles distributed on the atom sites. Dipole-dipole, dipole-quadrupole, and quadrupole-quadrupole distributed polarizabilities are used to represent the response of the multipoles to an electric field. We compare the model against two large databases consisting of 43,844 3-body terms and 3,603 4-body terms obtained from high level ab initio calculations previously used to fit the MB-pol and q-AQUA classical interaction potentials for water. The classical induction model with no adjustable parameters reproduces the ab initio 3-/4-body terms contained in these two databases with a root-mean-square error (RMSE) of 0.104/0.058 and a mean-absolute error (MAE) of 0.054/0.026 kcal/mol, respectively. These results are on par with the ones obtained by fitting the same data using over 14,000 (for the 3-body) and 200 (for the 4-body) parameters via Permutationally Invariant Polynomials (PIPs). This demonstrates the accuracy of this physically motivated model in describing the 3- and 4-body terms in the interactions between water molecules with no adjustable parameters. The triple-dipole-dispersion energy, included in the calculation of the 3-body energy, was found to be small but not quite negligible. The model represents a practical, efficient, and transferable approach for obtaining accurate nonadditive interactions for multicomponent systems without the need to perform tens of thousands of high level electronic structure calculations and fitting them with PIPs.

Bonding, Thermodynamics, and Spectroscopy of the Metal Borides UB0/+/– and WB0/+/–

The bonding and spectroscopy of the UB0/+/- and WB0/+/- molecules were examined by performing high-level electronic structure calculation on their low-lying electronic states. The calculations were performed at the SO-CASPT2 level to obtain the low-lying excited states and at the FPD level to calculate the adiabatic electronic affinities (AEA), ionization energies (IE), and bond dissociation energies (BDE). Compared to UC and UN, UB has a much denser manifold of states below 1.7 eV. The ground state of UB is predicted to be 8I5/2, and that of WB is 6Π7/2. The calculated IEs of UB and WB are 6.241 and 7.314 eV, respectively, and the corresponding AEAs are 1.160 and 1.422 eV. The BDE of UB is predicted to be 223.1 kJ/mol, which is considerably lower than those predicted for UC and UN and ∼35 kJ/mol lower than the BDE of WB. NBO calculations show that the U and B are connected by two 1-electron π bonds and one 1-electron σ bond with substantial ionic character and a bond order of 1.5. There are three unpaired electrons in the 5f on U. WB has less ionic character than UB with a doubly occupied π bond and a singly occupied σ bond for a bond order of ∼1.5. The results show that the U in UB behaves more like an actinide and the W in WB more like a transition metal.

Transferable Potential Function for Flexible H2O Molecules Based on the Single-Center Multipole Expansion.

A potential function is presented for describing a system of flexible H2O molecules based on the single-center multipole expansion (SCME) of the electrostatic interaction. The model, referred to as SCME/f, includes the variation of the molecular quadrupole moment as well as the dipole moment with changes in bond length and angle so as to reproduce results of high-level electronic structure calculations. The multipole expansion also includes fixed octupole and hexadecapole moments, as well as anisotropic dipole-dipole, dipole-quadrupole, and quadrupole-quadrupole polarizability tensors. The model contains five adjustable parameters related to the repulsive interaction and damping functions in the electrostatic and dispersion interactions. Their values are adjusted to reproduce the lowest energy isomers of small clusters, (H2O)n with n = 2-6, as well as measured properties of the ice Ih crystal. Subsequent calculations of the energy difference between the various isomer configurations of the clusters show that SCME/f gives good agreement with results of electronic structure calculations and represents a significant improvement over the previously presented rigid SCME potential function. Analysis of the vibrational frequencies of the clusters and structural properties of ice Ih crystal show the importance of accurately describing the variation of the quadrupole moment with molecular structures.

Vibronic coupling in the ground and excited states of the imidazole radical cation.

Vibronic interactions in the ground and two excited states of the imidazole radical cation, X2A″ (π-1), A2A' (nσ-1), and B2A″ (π-1), and the associated nuclear dynamics were studied theoretically. The results were used to interpret the recent photoelectron measurements [M. Patanen et al., J. Chem. Phys. 155, 054304 (2021)]. The present high-level electronic structure calculations employing, in particular, the single, double, and triple excitations and equation-of-motion coupled-cluster method accounting for single and double excitation approaches and complete basis set extrapolation technique for the evaluation of the vertical ionization energies of imidazole indicate that the A 2A' and B 2A″ states are very close in energy and subject to non-adiabatic effects. Our modeling confirms the existence of pronounced vibronic coupling of the A 2A' and B 2A″ states. Moreover, despite the large energy gap of nearly 1.3eV, the ground state X 2A″ is efficiently coupled to the A 2A' state. The modeling was performed within the framework of the three-state linear vibronic coupling problem employing Hamiltonians expressed in a basis of diabatic electronic states and parameters derived from ab initio calculations. The ionization spectrum was computed using the multi-configuration time-dependent Hartree method. The calculated spectrum is in good agreement with the experimental data, allowing for some interpretation of the observed features to be proposed.

Electronic Properties of UN and UN- from Photoelectron Spectroscopy and Correlated Molecular Orbital Theory.

The results of calculations of the properties of the anion UN- including electron detachment are described, which further expand our knowledge of this diatomic molecule. High-level electronic structure calculations were conducted for the UN and UN- diatomic molecules and compared to photoelectron spectroscopy measurements. The low-lying Ω states were obtained using multireference CASPT2 including spin-orbit effects up to ∼20,000 cm-1. At the Feller-Peterson-Dixon (FPD) level, the adiabatic electron affinity (AEA) of UN is estimated to be 1.402 eV and the vertical detachment energy (VDE) is 1.423 eV. The assignment of the UN excited states shows good agreement with the experimental results with a VDE of 1.424 eV. An Ω = 4 ground state was obtained for UN- which is mainly associated with the 3H ΛS state. Thermochemical calculations estimate a bond dissociation energy (BDE) for UN- (U- + N) of 665.9 kJ/mol, ∼15% larger than that of UN and UN+. The NBO analysis reveals U-N triple bonds for the UN, UN-, and UN+ species.

Experimental and kinetic modeling study of α-methylnaphthalene laminar flame speeds

α-Methylnaphthalene (AMN) is the primary reference bicyclic aromatic compound of diesel, and it is commonly used as a component of diesel, kerosene and jet-fuel surrogates formulated to describe real fuel combustion kinetics. However, few experimental data on neat AMN combustion are available in the literature. This work provides the first measurements of laminar flame speed profiles of AMN/air mixtures at 1 bar varying the initial temperature from 425 to 484 K, and equivalence ratio (φ) between 0.8 and 1.35 paving the way for the kinetic study of AMN combustion chemistry at high temperatures (>1800 K). The experimental data obtained in a spherical reactor are compared with kinetic model simulations. Specifically, the AMN kinetics is implemented from its analogous monocyclic aromatic compound, i.e., toluene, through the analogy and rate rule approach. This method allows to develop kinetic mechanisms of large species from the kinetics of smaller ones characterized by analogous chemical features, namely the aromaticity and the methyl functionality in the case of toluene and AMN. In doing so, it is possible to overcome the need of high-level electronic structure calculations for the evaluation of rate constants, as their computational cost increases exponentially with the number of heavy atoms of the selected species. To assess the validity of this approach, ab initio calculations are performed to derive the rate constants of the H-atom abstraction reactions by H, OH and CH3 radicals from both toluene and AMN. The kinetic model obtained satisfactorily agrees with the measured laminar flame speed profiles. Sensitivity and flux analyses are performed to investigate similarities and differences between the main reaction channels of toluene and AMN combustion, with the former leading to ∼6 cm/s faster flame speed at almost identical conditions (P=1 bar, T∼425 K), as evidenced by both kinetic model simulations and experimental findings.

The competitive mechanism between photoisomerization and excited state intramolecular proton transfer process of 2′-Hydroxychalcone system

The photoisomerization and excited state intramolecular proton transfer (ESIPT) are the most common processes in molecular photoswitches. Their coexistence and competing relationship in molecules usually make the deactivation process of the molecules become complex. In the current work, we study the underlying deactivation mechanism of trans-form 2′-hydroxychalcone (2′HC), which possesses both photoisomerization and ESIPT in the excited state, by combining high-level electronic structure calculations and on-the-fly surface hopping dynamics simulations. Four minimum energy conical intersections (MECIs) are found to be involved in the whole deactivation process. Following excitation to the S3 state of the most stable trans-enol tautomer, a strong coupling from the ππ* onto the nπ* state facilitates the ultrafast S3/S1 internal conversion process through an intricate conical intersection seam among S1, S2 and S3 state. The subsequent S1 to S0 state relaxation pathway is divided into two branches. The first process is initiated by twisting motion of C8─C9 bridging bond, which decays directly to the ground state via enol MECI. The other one is triggered by an ultrafast ESIPT process firstly and followed by twisting motion of the C1─C7 bond, leading the system funnel to the ground state by a keto type MECI, and finally generates the precursor of coloured flavanone. The proposed S3→(S2) S1 → S0 two step decay pattern is consistent with previous experimental observations. At the molecular microscopic level, the CO bond alternation motion plays a vital role in the whole relaxation process. Our results indicate that further practical application of 2′HC as molecular photoswitches can be achieved by modifying the molecular structure to enhance the ESIPT process.

Accurate spectroscopy, dipole moment, and ionization energy of gadolinium monoxide from high-level electronic structure calculations

A complete-basis-set (CBS) coupled-cluster composite approach including core correlation, spin–orbit coupling, and higher-order correlation up to CCSDT(Q) is used to determine the GdO and GdO+ bond dissociation energies (BDE) and GdO ionization energy (IE). Composite BDE(GdO+) and IE(GdO) are superior in accuracy to their experimental counterparts, differing from the latter by more than 0.3 eV. The CBS CCSD(T) spectroscopic constants re, ωe, ωexe, and αe of GdO and GdO+ and dipole moment of GdO are reported for the first time.

Observation of intermolecular Coulombic decay and shake-up satellites in liquid ammonia.

We report the first nitrogen 1s Auger–Meitner electron spectrum from a liquid ammonia microjet at a temperature of ∼223 K (–50 °C) and compare it with the simultaneously measured spectrum for gas-phase ammonia. The spectra from both phases are interpreted with the assistance of high-level electronic structure and ab initio molecular dynamics calculations. In addition to the regular Auger–Meitner-electron features, we observe electron emission at kinetic energies of 374–388 eV, above the leading Auger–Meitner peak (3a12). Based on the electronic structure calculations, we assign this peak to a shake-up satellite in the gas phase, i.e., Auger–Meitner emission from an intermediate state with additional valence excitation present. The high-energy contribution is significantly enhanced in the liquid phase. We consider various mechanisms contributing to this feature. First, in analogy with other hydrogen-bonded liquids (noticeably water), the high-energy signal may be a signature for an ultrafast proton transfer taking place before the electronic decay (proton transfer mediated charge separation). The ab initio dynamical calculations show, however, that such a process is much slower than electronic decay and is, thus, very unlikely. Next, we consider a non-local version of the Auger–Meitner decay, the Intermolecular Coulombic Decay. The electronic structure calculations support an important contribution of this purely electronic mechanism. Finally, we discuss a non-local enhancement of the shake-up processes.

Molecular Properties of Thorium Hydrides: Electron Affinities and Thermochemistry.

High-level electronic structure calculations of the ground and low-lying energy electronic states for ThHx and ThHx- for x = 2-5 are reported and compared to available anion photoelectron detachment experiments. The adiabatic electron affinities (EAs) are predicted to be 0.82, 0.88, 0.51, and 2.36 eV for x = 2 to 5, respectively, at the Feller-Peterson-Dixon (FPD) level. The vertical detachment energies (VDEs) are predicted to be 0.84, 0.88, 0.81, and 4.38 eV for x = 2-5, respectively. The corresponding experimental VDEs are 0.871 eV for x = 2, 0.88 eV for x = 3, and 4.09 eV for x = 5. As for ThH, there is a significant spin-orbit (SO) correction for the EA of ThH2, and this correction decreases substantially for x > 2. The observed ThH2- photoelectron spectrum has many transitions as predicted at the CASPT2-SO level. The FPD bond dissociation energies (BDEs) increase from 67 to 75 kcal/mol for x = 2 to x = 4 at the FPD level. The BDE for ThH5 is much lower as it is a complex of H2 with ThH3. The hydride affinities for x = 2 to 4 are all comparable and near 70 kcal/mol. A natural bond orbital analysis is consistent with a significant Th+-H- ionic contribution to the Th-H bonds. There is very little participation of the 5f orbitals in the bonding and the valence electrons on the Th are dominated by 7s and 6d for the neutrals and anions except for ThH2- where there is a significant contribution from the 7p.

High Level Electronic Structure Calculation of Molecular Solid-State NMR Shielding Constants.

In this work, we present a quantum mechanics/molecular mechanics (QM/MM) approach for the computation of solid-state nuclear magnetic resonance (SS-NMR) shielding constants (SCs) for molecular crystals. Besides applying standard-DFT functionals like GGAs (PBE), meta-GGAs (TPSS), and hybrids (B3LYP), we apply a double-hybrid (DSD-PBEP86) functional as well as MP2, using the domain-based local pair natural orbital (DLPNO) formalism, to calculate the NMR SCs of six amino acid crystals. All the electronic structure methods used exhibit good correlation of the NMR shieldings with respect to experimental chemical shifts for both 1H and 13C. We also find that local electronic structure is much more important than the long-range electrostatic effects for these systems, implying that cluster approaches using all-electron/Gaussian basis set methods might offer great potential for predictive computations of solid-state NMR parameters for organic solids.

Photodissociation dynamics of N3.

The photodissociation dynamics of N3 + excited from its (linear) 3Σg -/(bent) 3A″ ground to the first excited singlet and triplet states is investigated. Three-dimensional potential energy surfaces for the 1A', 1A″, and 3A' electronic states, correlating with the 1Δg and 3Πu states in linear geometry, for N3 + are constructed using high-level electronic structure calculations and represented as reproducing kernels. The reference ab initio energies are calculated at the MRCI+Q/aug-cc-pVTZ level of theory. For following the photodissociation dynamics in the excited states, rotational and vibrational distributions P(v') and P(j') for the N2 product are determined from vertically excited ground state distributions. Due to the different shapes of the ground state 3A″ potential energy surface and the excited states, appreciable angular momentum j' ∼ 60 is generated in diatomic fragments. The lifetimes in the excited states extend to at least 50ps. Notably, results from sampling initial conditions from a thermal ensemble and from the Wigner distribution of the ground state wavefunction are comparable.

Interaction of Th with H0/-/+: Combined Experimental and Theoretical Thermodynamic Properties.

High-level electronic structure calculations of the low-lying energy electronic states for ThH, ThH-, and ThH+ are reported and compared to experimental measurements. The inclusion of spin-orbit coupling is critical to predict the ground-state ordering as inclusion of spin-orbit switches the coupled-cluster CCSD(T) ordering of the two lowest energy states for ThH and ThH+. At the multireference spin-orbit SO-CASPT2 level, the ground states of ThH, ThH-, and ThH+ are predicted to be the 2Δ3/2, 3Φ2, and 3Δ1 states, respectively. The adiabatic electron affinity is calculated to be 0.820 eV, and the vertical detachment energy is calculated to be 0.832 eV in comparison to an experimental value of 0.87 ± 0.02 eV. The observed ThH- photoelectron spectrum has many transitions, which approximately correlate with excitations of Th+ and/or Th. The adiabatic ionization energy of ThH including spin-orbit corrections is calculated to be 6.181 eV. The natural bond orbital results are consistent with a significant contribution of the Th+H- ionic configuration to the bonding in ThH. The bond dissociation energies for ThH, ThH-, and ThH+ using the Feller-Peterson-Dixon approach were calculated to be similar for all three molecules and lie between 259 and 280 kJ/mol.

The role of the intermediate triplet state in iron-catalyzed multi-state C-H activation.

Efficient activation and functionalization of the C-H bond under mild conditions are of a great interest in chemical synthesis. We investigate the previously proposed spin-accelerated activation of the C(sp2)-H bond by a Fe(II)-based catalyst to clarify the role of the intermediate triplet state in the reaction mechanism. High-level electronic structure calculations on a small model of a catalytic system utilizing the coupled cluster with the single, double, and perturbative triple excitations [CCSD(T)] are used to select the density functional for the full-size model. Our analysis indicates that the previously proposed two-state quintet-singlet reaction pathway is unlikely to be efficient due to a very weak spin-orbit coupling between these two spin states. We propose a more favorable multi-state quintet-triplet-singlet reaction pathway and discuss the importance of the intermediate triplet state. This triplet state facilitates a spin-accelerated reaction mechanism by strongly coupling to both quintet and singlet states. Our calculations show that the C-H bond activation through the proposed quintet-triplet-singlet reaction pathway is more thermodynamically favorable than the single-state quintet and two-state singlet-quintet mechanisms.

Radical-Radical Reaction Dynamics Probed Using Millimeterwave Spectroscopy: Propargyl + NH2/ND2.

We apply chirped-pulse uniform flow millimeterwave (CPUF-mmW) spectroscopy to study the complex multichannel reaction dynamics in the reaction between the propargyl and amino radicals (C3H3 + NH2/ND2), a radical-radical reaction of importance in the gas-phase chemistry of astrochemical environments and combustion systems. The photolytically generated radicals are allowed to react in a well-characterized quasi-uniform supersonic flow, and mmW rotational spectroscopy (70-93 GHz) is used for simultaneous detection of the reaction products: HCN, HNC, HC3N, DCN, DNC, and DC3N, while spectral intensities of the measured pure-rotational lines allow product branching to be quantified. High-level electronic structure calculations were used for theoretical prediction of the reaction pathways and branching. Experimentally deduced product branching fractions were compared with the results from statistical simulations based on the RRKM theory. Product branching was found to be strongly dependent on the excess internal energy of the C3H3 and NH2/ND2 reactants.