Analytical gradients for nuclear-electronic orbital multistate density functional theory: Geometry optimizations and reaction paths.

Hydrogen tunneling plays a critical role in many biologically and chemically important processes. The nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) method was developed to describe hydrogen transfer systems. In this approach, the transferring proton is treated quantum mechanically on the same level as the electrons within multicomponent DFT, and a nonorthogonal configuration interaction scheme is used to produce delocalized vibronic states from localized vibronic states.

Analytical Gradients for Nuclear-Electronic Orbital Time-Dependent Density Functional Theory: Excited-State Geometry Optimizations and Adiabatic Excitation Energies.

The computational investigation of photochemical processes often entails the calculation of excited-state geometries, energies, and energy gradients. The nuclear-electronic orbital (NEO) approach treats specified nuclei, typically protons, quantum mechanically on the same level as the electrons, thereby including the associated nuclear quantum effects and non-Born-Oppenheimer behavior into quantum chemistry calculations. The multicomponent density functional theory (NEO-DFT) and time-dependent DFT (NEO-TDDFT) methods allow efficient calculations of ground and excited states, respectively.

Transition states, reaction paths, and thermochemistry using the nuclear-electronic orbital analytic Hessian.

The nuclear-electronic orbital (NEO) method is a multicomponent quantum chemistry theory that describes electronic and nuclear quantum effects simultaneously while avoiding the Born-Oppenheimer approximation for certain nuclei. Typically specified hydrogen nuclei are treated quantum mechanically at the same level as the electrons, and the NEO potential energy surface depends on the classical nuclear coordinates. This approach includes nuclear quantum effects such as zero-point energy and nuclear delocalization directly into the potential energy surface.

Molecular Vibrational Frequencies with Multiple Quantum Protons within the Nuclear-Electronic Orbital Framework.

The nuclear-electronic orbital (NEO) approach treats all electrons and specified nuclei, typically protons, on the same quantum mechanical level. Proton vibrational excitations can be calculated using multicomponent time-dependent density functional theory (NEO-TDDFT) for fixed classical nuclei. Recently the NEO-DFT(V) approach was developed to enable the calculation of molecular vibrational frequencies for modes composed of both classical and quantum nuclei.

Diagonal Born-Oppenheimer Corrections within the Nuclear-Electronic Orbital Framework.

The nuclear-electronic orbital (NEO) method treats specified nuclei, typically protons, quantum mechanically on the same level as the electrons. This approach invokes the Born-Oppenheimer separation between the quantum and classical nuclei, as well as the conventional separation between the electrons and classical nuclei. To test the validity of this additional adiabatic approximation, herein the diagonal Born-Oppenheimer correction (DBOC) within the NEO framework is derived, analyzed, and calculated numerically for a set of eight molecules.

Brønsted Acid Scaling Relationships Enable Control Over Product Selectivity from O Reduction with a Mononuclear Cobalt Porphyrin Catalyst.

The selective reduction of O, typically with the goal of forming HO, represents a long-standing challenge in the field of catalysis. Macrocyclic transition-metal complexes, and cobalt porphyrins in particular, have been the focus of extensive study as catalysts for this reaction. Here, we show that the mononuclear Co-tetraarylporphyrin complex, Co(por) (por = meso-tetra(4-methoxyphenyl)porphyrin), catalyzes either 2e/2H or 4e/4H reduction of O with high selectivity simply by changing the identity of the Brønsted acid in dimethylformamide (DMF).

Molecular Vibrational Frequencies within the Nuclear-Electronic Orbital Framework.

A significant challenge for multicomponent quantum chemistry methods is the calculation of vibrational frequencies for comparison to experiment. The nuclear-electronic orbital (NEO) approach treats specified nuclei, typically key protons, quantum mechanically. The Born-Oppenheimer separation between the quantum and classical nuclei prevents the direct calculation of vibrational frequencies corresponding to modes composed of both types of nuclei.

Alternative forms and transferability of electron-proton correlation functionals in nuclear-electronic orbital density functional theory.

Multicomponent density functional theory (DFT) allows the consistent quantum mechanical treatment of both electrons and nuclei. Recently the epc17 electron-proton correlation functional was derived using a multicomponent extension of the Colle-Salvetti formalism and was implemented within the nuclear-electronic orbital (NEO) framework for treating electrons and specified protons quantum mechanically. Herein another electron-proton correlation functional, denoted epc18, is derived using a different form for the functional parameter interpreted as representing the correlation length for electron-proton interactions.

Kinetic and Mechanistic Characterization of Low-Overpotential, HO-Selective Reduction of O Catalyzed by NO-Ligated Cobalt Complexes.

A soluble, bis-ketiminate-ligated Co complex [Co(NO)] was recently shown to catalyze selective reduction of O to HO with an overpotential as low as 90 mV. Here we report experimental and computational mechanistic studies of the Co(NO)-catalyzed O reduction reaction (ORR) with decamethylferrocene (Fc*) as the reductant in the presence of AcOH in MeOH. Analysis of the Co/O binding stoichiometry and kinetic studies support an O reduction pathway involving a mononuclear cobalt species.