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We propose an efficient version of ensemble Hartree–Fock/density functional theory to calculate a set of two charge-transfer states for systems with odd-numbers of electrons. The approach does require definitions of donor/acceptor fragments; however, the approach is not very sensitive to such definitions—even in the limit of very strong electronic coupling. The key ansatz is that, by mandating that the vector space spanned by the active orbitals projects equally onto the donor and acceptor fragments, such a constraint eliminates all intra-molecular local excitations and makes it far easier to generate potential energy surfaces that are smooth over a wide region of configuration space. The method is fast, working with only two electron configurations, and should be useful for ab initio non-adiabatic dynamics in the near future. [ABSTRACT FROM AUTHOR]

Within the context of fewest-switch surface hopping (FSSH) dynamics, one often wishes to remove the angular component of the derivative coupling between states J and K . In a previous set of papers, Shu et al. [J. Phys. Chem. Lett. 11, 1135–1140 (2020)] posited one approach for such a removal based on direct projection, while we isolated a second approach by constructing and differentiating a rotationally invariant basis. Unfortunately, neither approach was able to demonstrate a one-electron operator O ̂ whose matrix element J O ̂ K was the angular component of the derivative coupling. Here, we show that a one-electron operator can, in fact, be constructed efficiently in a semi-local fashion. The present results yield physical insight into designing new surface hopping algorithms and are of immediate use for FSSH calculations. [ABSTRACT FROM AUTHOR]

The recently developed real-time nuclear–electronic orbital (RT-NEO) approach provides an elegant framework for treating electrons and selected nuclei, typically protons, quantum mechanically in nonequilibrium dynamical processes. However, the RT-NEO approach neglects the motion of the other nuclei, preventing a complete description of the coupled nuclear–electronic dynamics and spectroscopy. In this work, the dynamical interactions between the other nuclei and the electron–proton subsystem are described with the mixed quantum–classical Ehrenfest dynamics method. The NEO-Ehrenfest approach propagates the electrons and quantum protons in a time-dependent variational framework, while the remaining nuclei move classically on the corresponding average electron–proton vibronic surface. This approach includes the non-Born–Oppenheimer effects between the electrons and the quantum protons with RT-NEO and between the classical nuclei and the electron–proton subsystem with Ehrenfest dynamics. Spectral features for vibrational modes involving both quantum and classical nuclei are resolved from the time-dependent dipole moments. This work shows that the NEO-Ehrenfest method is a powerful tool to study dynamical processes with coupled electronic and nuclear degrees of freedom. [ABSTRACT FROM AUTHOR]

Multicomponent quantum chemistry allows the quantum mechanical treatment of electrons and specified protons on the same level. Typically the goal is to identify a self-consistent-field (SCF) solution that is the global minimum associated with the molecular orbital coefficients of the underlying Hartree-Fock (HF) or density functional theory (DFT) calculation. To determine whether the solution is a minimum or a saddle point, herein we derive the stability conditions for multicomponent HF and DFT in the nuclear-electronic orbital (NEO) framework. The gradient is always zero for an SCF solution, whereas the Hessian must be positive semi-definite for the solution to be a minimum rather than a saddle point. The stability matrices for NEO-HF and NEO-DFT have the same matrix structures, which are identical to the working matrices of their corresponding linear response time-dependent theories (NEO-TDHF and NEO-TDDFT) but with a different metric. A negative eigenvalue of the stability matrix is a necessary but not sufficient condition for the corresponding NEO-TDHF or NEO-TDDFT working equation to have an imaginary eigenvalue solution. Electron-proton systems could potentially exhibit three types of instabilities: electronic, protonic, and electron-proton vibronic instabilities. The internal and external stabilities for theories with different constraints on the spin and spatial orbitals can be analyzed. This stability analysis is a useful tool for characterizing SCF solutions and is helpful when searching for lower-energy solutions. Initial applications to HCN, HNC, and 2-cyanomalonaldehyde, in conjunction with NEO ∆SCF calculations, highlight possible connections between stationary points in nuclear coordinate space for conventional electronic structure calculations and stationary points in orbital space for NEO calculations. [ABSTRACT FROM AUTHOR]