The Self-Consistent Field and Bohr's Nuclear Model

R.V. Dzholos, В.Г. Соловьев

Gerhard Stock

A semiclassical time-dependent self-consistent-field approach for the description of dissipative quantum phenomena is proposed. The total density operator is approximated by a semiclassical ansatz, which couples the system degrees of freedom to the bath degrees of freedom in a self-consistent manner, and is thus in the spirit of a classical-path description. The capability of the approach is demonstrated by comparing semiclassical calculations for a spin–boson model with an Ohmic bath to exact path-integral calculations. It is shown that the semiclassical model nicely reproduces the complex dissipative behavior of the spin–boson model for a large range of model parameters. The validity and accuracy of the semiclassical approach is discussed in some detail. It is shown that the method is essentially based on the assumption of complete randomization of nuclear phases. In particular, the assumption of phase randomization allows one to perform the trace over the bath variables through quasiclassical sampling of the nuclear initial conditions without invoking any further approximation.

Peter Schuck, S. Ethofer

Jiaao Su, Wei Huang, Yinxuan Song +1 more

Accurate prediction of nuclear magnetic resonance (NMR) shielding constants for strongly correlated systems remains challenging. In this context, we present a density matrix renormalization group self-consistent-field (DMRG-SCF) implementation for NMR shielding calculations with large active spaces. Within a gauge-including atomic orbital DMRG-SCF (GIAO-DMRG-SCF) framework, we formulate and solve the coupled-perturbed DMRG-SCF (CP-DMRG-SCF) equations using local-site effective Hamiltonians. This approach enables the direct evaluation of the wave function's response to an external magnetic field. In the limit of small active spaces, the computed NMR shieldings are in agreement with conventional complete active space self-consistent-field (CASSCF) results, while the present approach naturally extends to larger active spaces inaccessible to standard multiconfigurational methods. Applications to a series of molecular systems, particularly strongly correlated transition metal complexes, demonstrate that the proposed implementation can be both reliable and accurate.

Ervin B. Podgoršak