Theoretical Study of the Dissociation Energy of First-Row Metallocenium Ions

The bond dissociation energy of a series of metallocenium ions, i.e., the energy difference of the reaction MCp₂⁺ → MCp⁺ + Cp· (with M = Ti, V, Cr, Mn, Fe, Co, and Ni), was studied by means of multiconfigurational perturbation theory (CASPT2, RASPT2, NEVPT2) and restricted coupled cluster theory (CCSD­(T)). From a comparison between the results obtained from these different methods, and a detailed analysis of their treatment of electron correlation effects, a set of MCp⁺–Cp binding energies are proposed with an accuracy of 5 kcal/mol. The computed results are in good agreement with the experimental data measured by threshold photoelectron photoion coincidence (TPEPICO) spectroscopy but disagree with the more recent threshold collision-induced dissociation (TCID) experiments

Cumulant Approximated Second-Order Perturbation Theory Based on the Density Matrix Renormalization Group for Transition Metal Complexes: A Benchmark Study

The complete active space second order perturbation theory (CASPT2) can be extended to larger active spaces by using the density matrix renormalization group (DMRG) as solver. Two variants are commonly used: the costly DMRG-CASPT2 with exact 4-particle reduced density matrix (4-RDM) and the cheaper DMRG-cu(4)-CASPT2 in which the 4-cumulant is discarded. To assess the accuracy and limitations of the latter variant DMRG-cu(4)-CASPT2 we study the spin state energetics of iron porphyrin Fe­(P) and its model compound FeL₂, a model for the active center of NiFe hydrogenase, and manganese-oxo porphyrin MnO­(P)⁺; a series of excited states of chromium hexacarbonyl Cr­(CO)₆; and the interconversion of two Cu₂O₂²⁺ isomers. Our results clearly show that PT2 on top of DMRG is essential in order to obtain quantitative results for transition metal complexes. Good results were obtained with DMRG-cu(4)-CASPT2 as compared to full CASPT2 and DMRG-CASPT2 in calculations with small- and medium-sized active spaces. In calculations with large-sized active spaces (∼30 active orbitals), the performance of DMRG-cu(4)-CASPT2 is less impressive due to the errors originating from both the finite number of renormalized states <i>m</i> and the 4-RDM approximation

Spin State Energetics in First-Row Transition Metal Complexes: Contribution of (3s3p) Correlation and Its Description by Second-Order Perturbation Theory

This paper presents an in-depth study of the performance of multiconfigurational second-order perturbation theory (CASPT2, NEVPT2) in describing spin state energetics in first-row transition metal (TM) systems, including bare TM ions, TM ions in a field of point charges (TM/PC), and an extensive series of TM complexes, where the main focus lies on the (3s3p) correlation contribution to the relative energies of different spin states. To the best of our knowledge, this is the first systematic NEVPT2 investigation of TM spin state energetics. CASPT2 has been employed in several previous studies but was regularly found to be biased toward high spin states. The bias was attributed to a too low value of the so-called IPEA shift ϵ, an empirical correction in the CASPT2 zeroth-order Hamiltonian with a standard value of 0.25 hartree. Based on comparisons with experiment (TM ions) and calculations with the multireference configuration interaction (TM ions and TM/PC systems) and coupled-cluster (TM complexes) methods, we demonstrate in this work that standard CASPT2 works well for valence correlation and that its bias toward high-spin states is caused by an erratic description of (3s3p) correlation effects. The latter problem only occurs for spin transitions involving a ligand field (de)­excitation, not in bare TM ions. At the same time the (3s3p) correlation contribution also becomes strongly ϵ dependent. The error can be reduced by increasing ϵ but only at the expense of deteriorating the CASPT2 description of valence correlation in the TM complexes. The alternative NEVPT2 method works well for bare TM and TM/PC systems, but its results for the TM complexes are disappointing, with large errors both for the valence and (3s3p) correlation contributions to the relative energies of different spin states

Toward Highly Accurate Spin State Energetics in First-Row Transition Metal Complexes: A Combined CASPT2/CC Approach

In previous work on the performance of multiconfigurational second-order perturbation theory (CASPT2) in describing spin state energetics in first-row transition metal systems [Pierloot et al. J. Chem. Theory Comput. 2017, 13, 537−553], we showed that standard CASPT2 works well for valence correlation but does not describe the metal semicore (3s3p) correlation effects accurately. This failure is partially responsible for the well-known bias toward high-spin states of CASPT2. In this paper, we expand our previous work and show that this bias could be partly removed with a combined CASPT2/CC approach: using high-quality CASPT2 with extensive correlation-consistent basis sets for valence correlation and low-cost CCSD­(T) calculations with minimal basis sets for the metal semicore (3s3p) correlation effects. We demonstrate that this approach is efficient by studying the spin state energetics of a series of iron complexes modeling important intermediates in oxidative catalytic processes in chemistry and biochemistry. On the basis of a comparison with bare CCSD­(T) results from this and previous work, the average error of the CASPT2/CC approach is estimated at around 2 kcal mol^–1 in favor of high spin states

Atomic Layer Deposition of Ruthenium on Ruthenium Surfaces: A Theoretical Study

Atomic layer deposition (ALD) of ruthenium using two ruthenium precursors, i.e., Ru­(C₅H₅)₂ (RuCp₂) and Ru­(C₅H₅)­(C₄H₄N) (RuCpPy), is studied using density functional theory. By investigating the reaction mechanisms on bare ruthenium surfaces, i.e., (001), (101), and (100), and H-terminated surfaces, an atomistic insight in the Ru ALD is provided. The calculated results show that on the Ru surfaces both RuCp₂ and RuCpPy can undergo dehydrogenation and ligand dissociation reactions. RuCpPy is more reactive than RuCp₂. By forming a strong bond between N of Py and Ru of the surface, RuCpPy can easily chemisorb on the surfaces. The reactions of RuCp₂ on the surfaces are less favorable as the adsorption is not strong enough. This could be a factor contributing to the higher growth-per-cycle of Ru using RuCpPy, as observed experimentally. By studying the adsorption on H-terminated Ru surfaces, we showed that H can prevent the adsorption of the precursors, thus inhibiting the growth of Ru. Our calculations indicate that the H content on the surface can have an impact on the growth-per-cycle. Finally, our simulations also demonstrate large impacts of the surface structure on the reaction mechanisms. Of the three surfaces, the (100) surface, which is the less stable and has a zigzag surface structure, is also the most reactive one

Spin State Energetics and Oxyl Character of Mn-Oxo Porphyrins by Multiconfigurational ab Initio Calculations: Implications on Reactivity

Important electromeric states in manganese-oxo porphyrins MnO­(P)⁺ and MnO­(PF₄)⁺ (porphyrinato or <i>meso</i>-tetrafluoroporphyrinato) have been investigated with correlated ab initio methods (CASPT2, RASPT2), focusing on their possible role in multistate reactivity patterns in oxygen transfer (OAT) reactions. Due to the lack of oxyl character, the Mn^V singlet ground state is kinetically inert. OAT reactions should therefore rather proceed through thermally accessible triplet and quintet states that have a more pronounced oxyl character. Two states have been identified as possible candidates: a Mn^V triplet state and a Mn^IVO­(L^•a_2<i>u</i>)⁺ quintet state. The latter state is high-lying in MnO­(P)⁺ but is stabilized by the substitutions of H by F at the <i>meso</i> carbons (where the a_2<i>u</i> orbital has a significant amplitude). Oxyl character and Mn–O bond weakening in these two states stems from the fact that the Mn–O π* orbitals become singly (triplet) or doubly occupied (quintet). Moreover, an important role for the reactivity of the triplet state is also likely to be played by the π bond that has an empty π* orbital, because of the manifest diradical character of this π bond, revealed by the CASSCF wave function. Interestingly, the diradical character of this bond increases when the Mn–O bond is stretched, while the singly occupied π* orbital looses its oxygen radical contribution. The RASPT2 results were also used as a benchmark for the description of excited state energetics and Mn–O oxyl character with a wide range of pure and hybrid density functionals. With the latter functionals both the Mn^V → Mn^IV promotion energy and the diradical character of the π bond (with empty π*) are found to be extremely dependent on the contribution of exact exchange. For this reason, pure functionals are to be preferred

OpenMolcas: From source code to insight

In this article we describe the OpenMolcas environment and invite the computational chemistry community to collaborate. The open-source project already includes a large number of new developments realized during the transition from the commercial MOLCAS product to the open-source platform. The paper initially describes the technical details of the new software development platform. This is followed by brief presentations of many new methods, implementations, and features of the OpenMolcas program suite. These developments include novel wave function methods such as stochastic complete active space self-consistent field, density matrix renormalization group (DMRG) methods, and hybrid multiconfigurational wave function and density functional theory models. Some of these implementations include an array of additional options and functionalities. The paper proceeds and describes developments related to explorations of potential energy surfaces. Here we present methods for the optimization of conical intersections, the simulation of adiabatic and nonadiabatic molecular dynamics and interfaces to tools for semiclassical and quantum mechanical nuclear dynamics. Furthermore, the article describes features unique to simulations of spectroscopic and magnetic phenomena such as the exact semiclassical description of the interaction between light and matter, various X-ray processes, magnetic circular dichroism and properties. Finally, the paper describes a number of built-in and add-on features to support the OpenMolcas platform with post calculation analysis and visualization, a multiscale simulation option using frozen-density embedding theory and new electronic and muonic basis sets