Electronic Free Energy Surface of the Nitrogen Dimer Using First-Principles Finite Temperature Electronic Structure Methods.

We use full configuration interaction and density matrix quantum Monte Carlo methods to calculate the electronic free energy surface of the nitrogen dimer within the free-energy Born-Oppenheimer approximation. As the temperature is raised from T = 0, we find a temperature regime in which the internal energy causes bond strengthening. At these temperatures, adding in the entropy contributions is required to cause the bond to gradually weaken with increasing temperature. We predict a thermally driven dissociation for the nitrogen dimer between 22,000 to 63,200 K depending on symmetries and basis set. Inclusion of more spatial and spin symmetries reduces the temperature required. The origin of these observations is explored using the structure of the density matrix at various temperatures and bond lengths.

Iron-Catalyzed Halogen Exchange of Trifluoromethyl Arenes*.

The facile production of ArCF2 X and ArCX3 from ArCF3 using catalytic iron(III)halides is reported, which constitutes the first iron-catalyzed halogen exchange for non-aromatic C-F bonds. Theoretical calculations suggest direct activation of C-F bonds by iron coordination. ArCX3 and ArCF2 X products of the reaction are synthetically valuable due to their diversification potential. In particular, chloro- and bromodifluoromethyl arenes (ArCF2 Cl, ArCF2 Br respectively) provide access to a myriad of difluoromethyl arene derivatives (ArCF2 R). To optimize for mono-halogen exchange, a statistical method called Design of Experiments was used. Optimized parameters were successfully applied to electron rich and electron deficient aromatic substrates, and to the late stage diversification of flufenoxuron, a commercial insecticide. These methods are highly practical, being run at convenient temperatures and using inexpensive common reagents.

The Influence of Redox-Innocent Donor Groups in Tetradentate Ligands Derived from o-Phenylenediamine: Electronic Structure Investigations with Nickel.

The continued development of redox-active ligands requires an understanding as to how ligand modifications and related factors affect the locus of redox activity and spin density in metal complexes. Here we describe the synthesis, characterization, and electronic structure of nickel complexes containing triaryl NNNN (1) and SNNS (2) ligands derived from o-phenylenediamine. The tetradentate ligands in 1 and 2 were investigated and compared to those in metal complexes with compositionally similar ligands to determine how ligand-centered redox properties change when redox-active flanking groups are replaced with redox-innocent NMe2 or SMe. A derivative of 2 in which the phenylene backbone was replaced with ethylene (3) was also prepared to interrogate the importance of o-phenylenediamine for ligand-centered redox activity. Cyclic voltammograms collected for 1 and 2 revealed two fully reversible ligand-centered redox events. Remarkably, several quasi-reversible ligand-centered redox waves were also observed for 3 despite the absence of the o-phenylenediamine subunit. Oxidizing 1 and 2 with silver salts containing different counteranions (BF4-, OTf-, NTf2-) allowed the electrochemically generated complexes to be analyzed as a function of different oxidation states using single-crystal X-ray diffraction (XRD), EPR spectroscopy, and S K-edge X-ray absorption spectroscopy. The experimental data are corroborated by DFT calculations, and together, they reveal how the location of unpaired spin density and electronic structure in singly and doubly oxidized salts of 1 and 2 varies depending on the coordinating ability of the counteranions and exogenous ligands such as pyridine.

Modulation of Fe-Fe distance and spin in diiron complexes using tetradentate ligands with different flanking donors.

Here we report the synthesis and characterization of diiron complexes containing triaryl N4 and N2S2 ligands derived from o-phenylenediamine. The complexes display significant differences in Fe-Fe distances and magnetic properties that depend on the identity of the flanking NMe2 and SMe donor groups.

The Sign Problem in Density Matrix Quantum Monte Carlo.

Density matrix quantum Monte Carlo (DMQMC) is a recently developed method for stochastically sampling the N-particle thermal density matrix to obtain exact-on-average energies for model and ab initio systems. We report a systematic numerical study of the sign problem in DMQMC based on simulations of atomic and molecular systems. In DMQMC, the density matrix is written in an outer product basis of Slater determinants. In principle, this means that DMQMC needs to sample a space that scales in the system size, N, as O[(exp(N))2]. In practice, removing the sign problem requires a total walker population that exceeds a system-dependent critical walker population (Nc), imposing limitations on both storage and compute time. We establish that Nc for DMQMC is the square of Nc for FCIQMC. By contrast, the minimum Nc in the interaction picture modification of DMQMC (IP-DMQMC) is only linearly related to the Nc for FCIQMC. We find that this difference originates from the difference in propagation of IP-DMQMC versus canonical DMQMC: the former is asymmetric, whereas the latter is symmetric. When an asymmetric mode of propagation is used in DMQMC, there is a much greater stochastic error and is thus prohibitively expensive for DMQMC without the interaction picture adaptation. Finally, we find that the equivalence between IP-DMQMC and FCIQMC seems to extend to the initiator approximation, which is often required to study larger systems with large basis sets. This suggests that IP-DMQMC offers a way to ameliorate the cost of moving between a Slater determinant space and an outer product basis.

Using Density Matrix Quantum Monte Carlo for Calculating Exact-on-Average Energies for ab Initio Hamiltonians in a Finite Basis Set.

We here apply the recently developed initiator density matrix quantum Monte Carlo (i-DMQMC) to a variety of atoms and molecules in vacuum. i-DMQMC samples the exact density matrix of a Hamiltonian at finite temperature and combines the accuracy of full configuration interaction quantum Monte Carlo (FCIQMC)-full configuration interaction (FCI) or exact energies in a finite basis set-with finite temperature. In order to explore the applicability of i-DMQMC for molecular systems, we choose to study a recently developed test set by Rubenstein and co-workers: Be, H2O, and H10 at near-equilibrium and stretched geometries. We find that, for Be and H2O, i-DMQMC delivers energies with submillihartree accuracy when compared with finite temperature FCI. For H2O and both geometries of H10, we examine the difference between FT-AFQMC and i-DMQMC, which, in turn, estimates the difference in canonical versus grand canonical energies. We close with two discussions: one of simulation settings (initiator error, the interaction picture, and different basis sets), and another of energy difference calculations in the form of specific heat capacity and ionization potential calculations.

Fully Quantum Embedding with Density Functional Theory for Full Configuration Interaction Quantum Monte Carlo.

We here develop a fully quantum embedded version of initiator full configuration interaction quantum Monte Carlo (i-FCIQMC) and apply it to study an ionic bond (lithium hydride, LiH) and a covalent bond (hydrogen flouride, HF) physisorbed to a benzene molecule. The embedding is performed using a recently developed Huzinaga projection operator approach, which affords good synergy with i-FCIQMC by minimizing the number of orbitals in the calculation. When considering the dissociation energy of these bonds into closed-shell ionic fragments, we find that i-FCIQMC embedded in density functional theory (i-FCIQMC-in-DFT) delivers comparable accuracy with coupled cluster singles and doubles with perturbative triples embedded in density functional theory (CCSD(T)-in-DFT). In treating the bond dissociation energy curve of HF, i-FCIQMC-in-DFT has improved accuracy over CCSD(T)-in-DFT due to the presence of strong correlation. We discuss the implications of the new i-FCIQMC-in-DFT method as applied to bond breaking in catalysis.