*J Chem Phys ; 152(6): 064105, 2020 Feb 14.*

##### RESUMO

We develop several configuration interaction approaches for characterizing the electronic structure of an adsorbate on a metal surface (at least in model form). When one can separate the adsorbate from the substrate, these methods can achieve a reasonable description of adsorbate on-site electron-electron correlation in the presence of a continuum of states. While the present paper is restricted to the Anderson impurity model, there is hope that these methods can be extended to ab initio Hamiltonians and provide insight into the structure and dynamics of molecule-metal surface interactions.

*J Chem Theory Comput ; 16(2): 835-846, 2020 Feb 11.*

##### RESUMO

We investigate a simple and robust scheme for choosing the phases of adiabatic electronic states smoothly (as a function of geometry) so as to maximize the performance of ab initio non-adiabatic dynamics methods. Our approach is based upon consideration of the overlap matrix (U) between basis functions at successive points in time and selecting the phases so as to minimize the matrix norm of log(U). In so doing, one can extend the concept of parallel transport to cases with sharp curve crossings. We demonstrate that this algorithm performs well under extreme situations where dozens of states cross each other either through trivial crossings (where there is zero effective diabatic coupling), or through non-trivial crossings (when there is a non-zero diabatic coupling), or through a combination of both. In all cases, we compute the time-derivative coupling matrix elements (or equivalently non-adiabatic derivative coupling matrix elements) that are as smooth as possible. Our results should be of interest to all who are interested in either non-adiabatic dynamics, or more generally, parallel transport in large systems.

*J Chem Phys ; 150(16): 164105, 2019 Apr 28.*

##### RESUMO

It is well-known that under conditions of fast electronic equilibration and weak nonadiabaticity, nonadiabatic effects induced by electron-hole pair excitations can be partly incorporated through a frictional force. However, ab initio computation of the electronic friction tensor suffers from numerical instability and usually demands a convergence check. In this study, we present an efficient and accurate interpolation method for computing the electronic friction tensor in a nearly black-box manner as appropriate for molecular dynamics. In almost all cases, our method agrees quite well with the exact friction tensor which is available for several quadratic Hamiltonians. As such, we outperform more conventional approaches that are based on the introduction of a broadening parameter. Future work will implement this interpolation approach within ab initio software packages.

*J Chem Phys ; 146(24): 244110, 2017 Jun 28.*

##### RESUMO

Traditional ab initio electronic structure calculations of periodic systems yield delocalized eigenstates that should be understood as adiabatic states. For example, excitons are bands of extended states which superimpose localized excitations on every lattice site. However, in general, in order to study the effects of nuclear motion on exciton transport, it is standard to work with a localized description of excitons, especially in a hopping regime; even in a band regime, a localized description can be helpful. To extract localized excitons from a band requires essentially a diabatization procedure. In this paper, three distinct methods are proposed for such localized diabatization: (i) a simple projection method, (ii) a more general Pipek-Mezey localization scheme, and (iii) a variant of Boys diabatization. Approaches (i) and (ii) require localized, single-particle Wannier orbitals, while approach (iii) has no such dependence. These methods should be very useful for studying energy transfer through solids with ab initio calculations.