Towards a Holomorphic Density Functional Theory.

Self-consistent-field (SCF) approximations formulated using Hartree-Fock (HF) or Kohn-Sham density-functional theory (KS-DFT) have the potential to yield multiple solutions. However, the formal relationship between multiple solutions identified using HF or KS-DFT remains generally unknown. We investigate the connection between multiple SCF solutions for HF or KS-DFT by introducing a parameterized functional that scales between the two representations.

The Conveyor Belt Umbrella Sampling (CBUS) Scheme: Principle and Application to the Calculation of the Absolute Binding Free Energies of Alkali Cations to Crown Ethers.

We recently introduced a method called conveyor belt (CB) thermodynamic integration (TI) for the calculation of alchemical free-energy differences based on molecular dynamics simulations. In the present work, the CBTI approach is generalized to conformational free-energy changes, i.e.

Revisiting nuclear tunnelling in the aqueous ferrous-ferric electron transfer.

The aqueous ferrous-ferric system provides a classic example of an electron-transfer process in solution. There has been a long standing argument spanning more than three decades around the importance of nuclear tunnelling in this system, with estimates based on Wolynes theory suggesting a quantum correction factor of 65, while estimates based on a related spin-boson model suggest a smaller factor of 7-36. Recently, we have shown that Wolynes theory can break down for systems with multiple transition states leading to an overestimation of the rate, and we suggest that a liquid system such as the one investigated here may be particularly prone to this.