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At least 649 records · Page 36

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DOE OSTI2022

Modeling receptor flexibility in the structure-based design of KRAS G12C inhibitors

KRAS has long been referred to as an ‘undruggable’ target due to its high affinity for its cognate ligands (GDP and GTP) and its lack of readily exploited allosteric binding pockets. Recent progress in the development of covalent inhibitors of KRAS G12C has revealed that occupancy of an allosteric binding site located between the α3-helix and switch-II loop of KRAS G12C —sometimes referred to as the ‘switch-II pocket’—holds great potential in the design of direct inhibitors of KRAS G12C . In studying diverse switch-II pocket binders during the development of sotorasib (AMG 510), the first FDA-approved inhibitor of KRAS G12C , we found the dramatic conformational flexibility of the switch-II pocket posing significant challenges toward the structure-based design of inhibitors. Here, we present our computational approaches for dealing with receptor flexibility in the prediction of ligand binding pose and binding affinity. For binding pose prediction, we modified the covalent docking program CovDock to allow for protein conformational mobility. This new docking approach, termed as FlexCovDock, improves success rates from 55 to 89% for binding pose prediction on a dataset of 10 cross-docking cases and has been prospectively validated across diverse ligand chemotypes. For binding affinity prediction, we found standard free energy perturbation (FEP) methods could not adequately handle the significant conformational change of the switch-II loop. We developed a new computational strategy to accelerate conformational transitions through the use of targeted protein mutations. Using this methodology, the mean unsigned error (MUE) of binding affinity prediction were reduced from 1.44 to 0.89 kcal/mol on a set of 14 compounds. These approaches were of significant use in facilitating the structure-based design of KRAS G12C inhibitors and are anticipated to be of further use in the design of covalent (and noncovalent) inhibitors of other conformationally labile protein targets.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2012

Propagation of nonlinear coherent structures in a collisional magnetoplasma with nonthermal electrons and finite ion temperature

Nonlinear electrostatic waves in dissipative magnetized electron-ion (e-i) plasmas are investigated employing the two fluid model. In this regard, Zakharov Kuznetsov Burgers (ZKB) equation is derived using the small amplitude perturbation expansion method. It is observed that the nonthermal electron population, obliqueness, ion thermal effects, and kinematic viscosity significantly alter the structure of obliquely propagating nonlinear ion acoustic shock waves in dissipative e-i magnetoplasmas. It is observed that the system can admit both compressive and rarefactive shocks. The condition for the formation of both types of shocks is also given. The present study may be useful to understand the nonlinear propagation characteristics of electrostatic shock structures in space environments where the nonthermal electrons have been observed by various satellite missions such as Voyager and Freja.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2011

Isotope shifts and relativistic shifts of Cr ii for the study of {alpha} variation in quasar absorption spectra

We use the combination of configuration interaction and the many-body perturbation theory method (CI + MBPT) to perform ab initio calculations of the low-energy spectra of Cr ii with high accuracy. It is found that second-order MBPT diagrams should be included in a consistent and complete way for the MBPT to improve the accuracy of calculations in this five-valence-electron system. This contrasts with previous ions with fewer valence electrons, where it was found that single-valence-electron diagrams dominate the corrections. Isotope shifts and relativistic shifts (q values) are calculated for use in astronomical determination of the fine-structure constant in quasar absorption spectra.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2014

Thermodynamic of fluids from a general equation of state: The molecular discrete perturbation theory

An extensive generalisation of the discrete perturbation theory for molecular multipolar non-spherical fluids is presented. An analytical expression for the Helmholtz free energy for an equivalent discrete potential is given as a function of density, temperature, and intermolecular parameters with implicit shape and multipolar dependence. By varying the intermolecular parameters through their geometrical and multipolar dependence, a set of molecular fluids are considered and their vapor–liquid phase diagrams are tested against available simulation data. Concretely, multipolar and non-polar Kihara and chainlike fluids are tested and it is found that this theoretical approach is able to reproduce qualitatively and quantitatively well the Monte Carlo data for the selected molecular potentials, except near the critical region.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2013

Adapting SAFT-γ perturbation theory to site-based molecular dynamics simulation. I. Homogeneous fluids

In this work, we aim to develop a version of the Statistical Associating Fluid Theory (SAFT)-γ equation of state (EOS) that is compatible with united-atom force fields, rather than experimental data. We rely on the accuracy of the force fields to provide the relation to experimental data. Although, our objective is a transferable theory of interfacial properties for soft and fused heteronuclear chains, we first clarify the details of the SAFT-γ approach in terms of site-based simulations for homogeneous fluids. We show that a direct comparison of Helmholtz free energy to molecular simulation, in the framework of a third order Weeks-Chandler-Andersen perturbation theory, leads to an EOS that takes force field parameters as input and reproduces simulation results for Vapor-Liquid Equilibria (VLE) calculations. For example, saturated liquid density and vapor pressure of n-alkanes ranging from methane to dodecane deviate from those of the Transferable Potential for Phase Equilibria (TraPPE) force field by about 0.8% and 4%, respectively. Similar agreement between simulation and theory is obtained for critical properties and second virial coefficient. The EOS also reproduces simulation data of mixtures with about 5% deviation in bubble point pressure. Extension to inhomogeneous systems and united-atom site types beyond those used in description of n-alkanes will be addressed in succeeding papers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Probing the structural and dynamical properties of liquid water with models including non-local electron correlation

Water is a ubiquitous liquid that displays a wide range of anomalous properties and has a delicate structure that challenges experiment and simulation alike. The various intermolecular interactions that play an important role, such as repulsion, polarization, hydrogen bonding, and van der Waals interactions, are often difficult to reproduce faithfully in atomistic models. Here, electronic structure theories including all these interactions at equal footing, which requires the inclusion of non-local electron correlation, are used to describe structure and dynamics of bulk liquid water. Isobaric-isothermal (NpT) ensemble simulations based on the Random Phase Approximation (RPA) yield excellent density (0.994 g/ml) and fair radial distribution functions, while various other density functional approximations produce scattered results (0.8-1.2 g/ml). Molecular dynamics simulation in the microcanonical (NVE) ensemble based on Møller-Plesset perturbation theory (MP2) yields dynamical properties in the condensed phase, namely, the infrared spectrum and diffusion constant. At the MP2 and RPA levels of theory, ice is correctly predicted to float on water, resolving one of the anomalies as resulting from a delicate balance between van der Waals and hydrogen bonding interactions. For several properties, obtaining quantitative agreement with experiment requires correction for nuclear quantum effects (NQEs), highlighting their importance, for structure, dynamics, and electronic properties. A computed NQE shift of 0.6 eV for the band gap and absorption spectrum illustrates the latter. Giving access to both structure and dynamics of condensed phase systems, non-local electron correlation will increasingly be used to study systems where weak interactions are of paramount importance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Monte Carlo simulation and equation of state for flexible charged hard-sphere chain fluids: Polyampholyte and polyelectrolyte solutions

The thermodynamic modeling of flexible charged hard-sphere chains representing polyampholyte or polyelectrolyte molecules in solution is considered. The excess Helmholtz energy and osmotic coefficients of solutions containing short polyampholyte and the osmotic coefficients of solutions containing short polyelectrolytes are determined by performing canonical and isobaric-isothermal Monte Carlo simulations. A new equation of state based on the thermodynamic perturbation theory is also proposed for flexible charged hard-sphere chains. For the modeling of such chains, the use of solely the structure information of monomer fluid for calculating the chain contribution is found to be insufficient and more detailed structure information must therefore be considered. Two approaches, i.e., the dimer and dimer-monomer approaches, are explored to obtain the contribution of the chain formation to the Helmholtz energy. By comparing with the simulation results, the equation of state with either the dimer or dimer-monomer approach accurately predicts the excess Helmholtz energy and osmotic coefficients of polyampholyte and polyelectrolyte solutions except at very low density. It also well captures the effect of temperature on the thermodynamic properties of these solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

Observational constraints on K-inflation models

We extend the ModeCode software of Mortonson, Peiris and Easther [1] to enable numerical computation of perturbations in K-inflation models, where the scalar field no longer has a canonical kinetic term. Focussing on models where the kinetic and potential terms can be separated into a sum, we compute slow-roll predictions for various models and use these to verify the numerical code. A Markov chain Monte Carlo analysis is then used to impose constraints from WMAP7 data on the addition of a term quadratic in the kinetic energy to the Lagrangian of simple chaotic inflation models. For a quadratic potential, the data do not discriminate against addition of such a term, while for a quartic (λφ{sup 4}) potential inclusion of such a term is actually favoured. Overall, constraints on such a term from present data are found to be extremely weak.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2013

Resummed thermodynamic perturbation theory for bond cooperativity in associating fluids

We develop a resummed thermodynamic perturbation theory for bond cooperativity in associating fluids by extension of Wertheim's multi-density formalism. We specifically consider the case of an associating hard sphere with two association sites and both pairwise and triplet contributions to the energy, such that the first bond in an associated cluster receives an energy −ε{sup (1)} and each subsequent bond in the cluster receives an energy −ε{sup (2)}. To test the theory we perform new Monte Carlo simulations for potentials of this type. Theory and simulation are found to be in excellent agreement. We show that decreasing the energetic benefit of hydrogen bonding can actually result in a decrease in internal energy in the fluid. We also predict that when ε{sup (1)} = 0 and ε{sup (2)} is nonzero there is a transition temperature where the system transitions from a fluid of monomers to a mixture of monomers and very long chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Gas-phase Electronic Spectra of Coronene and Corannulene Cations

Gas-phase electronic spectra of the coronene (C{sub 24}H{sub 12}{sup +}) and corannulene (C{sub 20}H{sub 10}{sup +}) cations complexed with helium have been recorded in a quadrupole ion trap at 5 K by photodissociation. The electronic spectrum of C{sub 20}H{sub 10}{sup +} with two helium atoms was also measured to estimate the perturbation. This method is sufficient for an astronomical comparison because the shift due to the weakly bound helium is on the order of 0.2 Å. C{sub 24}H{sub 12}{sup +}--He has the origin band of the A{sup 2}E{sub 1g}←X{sup 2}E{sub 2u} transition at 9438.3 Å and that to a much higher state D{sub 3}←X{sup 2}E{sub 2u} at 4570 Å. The corannulene cation is subject to a Jahn–Teller distortion in the electronic ground state, leading to the 3{sup 2}A{sup ′}←X{sup 2}A{sup ′′} and 3{sup 2}A{sup ′′}←X{sup 2}A{sup ′} transitions with origin band maxima when complexed with helium at 5996.1 and 5882.6 Å. These absorptions lie in a region where there is a congestion of diffuse interstellar bands (DIBs). However, the recorded features have no match with astronomical observations, removing coronene and corannulene cations and probably other aromatic hydrocarbons of this size as possible carriers of the DIBs.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2014

Density functional theory for the description of spherical non-associating monomers in confined media using the SAFT-VR equation of state and weighted density approximations

As a first step of an ongoing study of thermodynamic properties and adsorption of complex fluids in confined media, we present a new theoretical description for spherical monomers using the Statistical Associating Fluid Theory for potential of Variable Range (SAFT-VR) and a Non-Local Density Functional Theory (NLDFT) with Weighted Density Approximations (WDA). The well-known Modified Fundamental Measure Theory is used to describe the inhomogeneous hard-sphere contribution as a reference for the monomer and two WDA approaches are developed for the dispersive terms from the high-temperature Barker and Henderson perturbation expansion. The first approach extends the dispersive contributions using the scalar and vector weighted densities introduced in the Fundamental Measure Theory (FMT) and the second one uses a coarse-grained (CG) approach with a unique weighted density. To test the accuracy of this new NLDFT/SAFT-VR coupling, the two versions of the theoretical model are compared with Grand Canonical Monte Carlo (GCMC) molecular simulations using the same molecular model. Only the version with the “CG” approach for the dispersive terms provides results in excellent agreement with GCMC calculations in a wide range of conditions while the “FMT” extension version gives a good representation solely at low pressures. Hence, the “CG” version of the theoretical model is used to reproduce methane adsorption isotherms in a Carbon Molecular Sieve and compared with experimental data after a characterization of the material. The whole results show an excellent agreement between modeling and experiments. Thus, through a complete and consistent comparison both with molecular simulations and with experimental data, the NLDFT/SAFT-VR theory has been validated for the description of monomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Computing the binding affinity of a ligand buried deep inside a protein with the hybrid steered molecular dynamics

Computing the ligand-protein binding affinity (or the Gibbs free energy) with chemical accuracy has long been a challenge for which many methods/approaches have been developed and refined with various successful applications. False positives and, even more harmful, false negatives have been and still are a common occurrence in practical applications. Inevitable in all approaches are the errors in the force field parameters we obtain from quantum mechanical computation and/or empirical fittings for the intra- and inter-molecular interactions. These errors propagate to the final results of the computed binding affinities even if we were able to perfectly implement the statistical mechanics of all the processes relevant to a given problem. And they are actually amplified to various degrees even in the mature, sophisticated computational approaches. In particular, the free energy perturbation (alchemical) approaches amplify the errors in the force field parameters because they rely on extracting the small differences between similarly large numbers. In this paper, we develop a hybrid steered molecular dynamics (hSMD) approach to the difficult binding problems of a ligand buried deep inside a protein. Sampling the transition along a physical (not alchemical) dissociation path of opening up the binding cavity- -pulling out the ligand- -closing back the cavity, we can avoid the problem of error amplifications by not relying on small differences between similar numbers. We tested this new form of hSMD on retinol inside cellular retinol-binding protein 1 and three cases of a ligand (a benzylacetate, a 2-nitrothiophene, and a benzene) inside a T4 lysozyme L99A/M102Q(H) double mutant. In all cases, we obtained binding free energies in close agreement with the experimentally measured values. This indicates that the force field parameters we employed are accurate and that hSMD (a brute force, unsophisticated approach) is free from the problem of error amplification suffered by many sophisticated approaches in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Vibrational circular dichroism from ab initio molecular dynamics and nuclear velocity perturbation theory in the liquid phase

We report the first fully ab initio calculation of dynamical vibrational circular dichroism spectra in the liquid phase using nuclear velocity perturbation theory (NVPT) derived electronic currents. Our approach is rigorous and general and thus capable of treating weak interactions of chiral molecules as, e.g., chirality transfer from a chiral molecule to an achiral solvent. We use an implementation of the NVPT that is projected along the dynamics to obtain the current and magnetic dipole moments required for accurate intensities. The gauge problem in the liquid phase is resolved in a twofold approach. The electronic expectation values are evaluated in a distributed origin gauge, employing maximally localized Wannier orbitals. In a second step, the gauge invariant spectrum is obtained in terms of a scaled molecular moments, which allows to systematically include solvent effects while keeping a significant signal-to-noise ratio. We give a thorough analysis and discussion of this choice of gauge for the liquid phase. At low temperatures, we recover the established double harmonic approximation. The methodology is applied to chiral molecules ((S)-d{sub 2}-oxirane and (R)-propylene-oxide) in the gas phase and in solution. We find an excellent agreement with the theoretical and experimental references, including the emergence of signals due to chirality transfer from the solute to the (achiral) solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Electron correlation within the relativistic no-pair approximation

This paper addresses the definition of correlation energy within 4-component relativistic atomic and molecular calculations. In the nonrelativistic domain the correlation energy is defined as the difference between the exact eigenvalue of the electronic Hamiltonian and the Hartree-Fock energy. In practice, what is reported is the basis set correlation energy, where the “exact” value is provided by a full Configuration Interaction (CI) calculation with some specified one-particle basis. The extension of this definition to the relativistic domain is not straightforward since the corresponding electronic Hamiltonian, the Dirac-Coulomb Hamiltonian, has no bound solutions. Present-day relativistic calculations are carried out within the no-pair approximation, where the Dirac-Coulomb Hamiltonian is embedded by projectors eliminating the troublesome negative-energy solutions. Hartree-Fock calculations are carried out with the implicit use of such projectors and only positive-energy orbitals are retained at the correlated level, meaning that the Hartree-Fock projectors are frozen at the correlated level. We argue that the projection operators should be optimized also at the correlated level and that this is possible by full Multiconfigurational Self-Consistent Field (MCSCF) calculations, that is, MCSCF calculations using a no-pair full CI expansion, but including orbital relaxation from the negative-energy orbitals. We show by variational perturbation theory that the MCSCF correlation energy is a pure MP2-like correlation expression, whereas the corresponding CI correlation energy contains an additional relaxation term. We explore numerically our theoretical analysis by carrying out variational and perturbative calculations on the two-electron rare gas atoms with specially tailored basis sets. In particular, we show that the correlation energy obtained by the suggested MCSCF procedure is smaller than the no-pair full CI correlation energy, in accordance with the underlying minmax principle and our theoretical analysis. We also show that the relativistic correlation energy, obtained from no-pair full MCSCF calculations, scales at worst as X{sup −2} with respect to the cardinal number X of our correlation-consistent basis sets optimized for the two-electron atoms. This is better than the X{sup −1} scaling suggested by previous studies, but worse than the X{sup −3} scaling observed in the nonrelativistic domain. The well-known 1/Z- expansion in nonrelativistic atomic theory follows from coordinate scaling. We point out that coordinate scaling for consistency should be accompanied by velocity scaling. In the nonrelativistic domain this comes about automatically, whereas in the relativistic domain an explicit scaling of the speed of light is required. This in turn explains why the relativistic correlation energy to the lowest order is not independent of nuclear charge, in contrast to nonrelativistic theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

On multichannel film dosimetry with channel-independent perturbations

Purpose: Different multichannel methods for film dosimetry have been proposed in the literature. Two of them are the weighted mean method and the method put forth byMicke et al. [“Multichannel film dosimetry with nonuniformity correction,” Med. Phys. 38, 2523–2534 (2011)] and Mayer et al. [“Enhanced dosimetry procedures and assessment for EBT2 radiochromic film,” Med. Phys. 39, 2147–2155 (2012)]. The purpose of this work was to compare their results and to develop a generalized channel-independent perturbations framework in which both methods enter as special cases. Methods: Four models of channel-independent perturbations were compared: weighted mean, Micke–Mayer method, uniform distribution, and truncated normal distribution. A closed-form formula to calculate film doses and the associated type B uncertainty for all four models was deduced. To evaluate the models, film dose distributions were compared with planned and measured dose distributions. At the same time, several elements of the dosimetry process were compared: film type EBT2 versus EBT3, different waiting-time windows, reflection mode versus transmission mode scanning, and planned versus measured dose distribution for film calibration and for γ-index analysis. The methods and the models described in this study are publicly accessible through IRISEU. Alpha 1.1 ( http://www.iriseu.com ). IRISEU. is a cloud computing web application for calibration and dosimetry of radiochromic films. Results: The truncated normal distribution model provided the best agreement between film and reference doses, both for calibration and γ-index verification, and proved itself superior to both the weighted mean model, which neglects correlations between the channels, and the Micke–Mayer model, whose accuracy depends on the properties of the sensitometric curves. With respect to the selection of dosimetry protocol, no significant differences were found between transmission and reflection mode scanning, between 75 ± 5 min and 20 ± 1 h waiting-time windows or between employing EBT2 or EBT3 films. Significantly better results were obtained when a measured dose distribution was used instead of a planned one as reference for the calibration, and when a planned dose distribution was used instead of a measured one as evaluation for the γ-analysis. Conclusions: The truncated normal distribution model of channel-independent perturbations was found superior to the other three models under comparison and the authors propose its use for multichannel dosimetry.

61 RADIATION PROTECTION AND DOSIMETRY↗

DOE OSTI2013

Constraints on the tensor-to-scalar ratio for non-power-law models

Recent cosmological observations hint at a deviation from the simple power-law form of the primordial spectrum of curvature perturbations. In this paper we show that in the presence of a tensor component, a turn-over in the initial spectrum is preferred by current observations, and hence non-power-law models ought to be considered. For instance, for a power-law parameterisation with both a tensor component and running parameter, current data show a preference for a negative running at more than 2.5σ C.L. As a consequence of this deviation from a power-law, constraints on the tensor-to-scalar ratio r are slightly broader. We also present constraints on the inflationary parameters for a model-independent reconstruction and the Lasenby and Doran (LD) model. In particular, the constraints on the tensor-to-scalar ratio from the LD model are: r{sub LD} = 0.11±0.024. In addition to current data, we show expected constraints from Planck-like and CMB-Pol sensitivity experiments by using Markov-Chain-Monte-Carlo sampling chains. For all the models, we have included the Bayesian Evidence to perform a model selection analysis. The Bayes factor, using current observations, shows a strong preference for the LD model over the standard power-law parameterisation, and provides an insight into the accuracy of differentiating models through future surveys.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2016

Structural, dynamical, and transport properties of the hydrated halides: How do At{sup −} bulk properties compare with those of the other halides, from F{sup −} to I{sup −}?

The properties of halides from the lightest, fluoride (F{sup −}), to the heaviest, astatide (At{sup −}), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force-field parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I{sup −} and At{sup −}, were computed in the gas phase using large and diffuse atomic basis sets, and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I{sup −} and At{sup −} in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F{sup −}, Cl{sup −}, and Br{sup −} ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At{sup −} in liquid water at ambient conditions to be 68 kcal mol{sup −1}, a value also close the I{sup −} one, about 70 kcal mol{sup −1}. In all, our simulation results for I{sup −} are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At{sup −} ion are predictive, as no theoretical or experimental data are available to date.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Assessment of the accuracy of coupled cluster perturbation theory for open-shell systems. I. Triples expansions

The accuracy at which total energies of open-shell atoms and organic radicals may be calculated is assessed for selected coupled cluster perturbative triples expansions, all of which augment the coupled cluster singles and doubles (CCSD) energy by a non-iterative correction for the effect of triple excitations. Namely, the second- through sixth-order models of the recently proposed CCSD(T–n) triples series [J. J. Eriksen et al., J. Chem. Phys. 140, 064108 (2014)] are compared to the acclaimed CCSD(T) model for both unrestricted as well as restricted open-shell Hartree-Fock (UHF/ROHF) reference determinants. By comparing UHF- and ROHF-based statistical results for a test set of 18 modest-sized open-shell species with comparable RHF-based results, no behavioral differences are observed for the higher-order models of the CCSD(T–n) series in their correlated descriptions of closed- and open-shell species. In particular, we find that the convergence rate throughout the series towards the coupled cluster singles, doubles, and triples (CCSDT) solution is identical for the two cases. For the CCSD(T) model, on the other hand, not only its numerical consistency, but also its established, yet fortuitous cancellation of errors breaks down in the transition from closed- to open-shell systems. The higher-order CCSD(T–n) models (orders n > 3) thus offer a consistent and significant improvement in accuracy relative to CCSDT over the CCSD(T) model, equally for RHF, UHF, and ROHF reference determinants, albeit at an increased computational cost.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗