Toward Linear Scaling Auxiliary-Field Quantum Monte Carlo with Local Natural Orbitals.

We develop a local correlation variant of auxiliary-field quantum Monte Carlo (AFQMC) based on local natural orbitals (LNO-AFQMC). In LNO-AFQMC, independent AFQMC calculations are performed for each localized occupied orbital using a truncated set of tailored orbitals. Because the size of this space does not grow with the system size for a target accuracy, the method has linear scaling.

Response properties in phaseless auxiliary field quantum Monte Carlo.

We present a method for calculating first-order response properties in phaseless auxiliary field quantum Monte Carlo by applying automatic differentiation (AD). Biases and statistical efficiency of the resulting estimators are discussed. Our approach demonstrates that AD enables the calculation of reduced density matrices with the same computational cost scaling per sample as energy calculations, accompanied by a cost prefactor of less than four in our numerical calculations.

Vibronic resonance is inadequately described by one-particle basis sets.

Vibrational-electronic (vibronic) resonance and its possible role in energy and charge transfer have been experimentally and theoretically investigated in several photosynthetic proteins. Using a dimer modeled on a typical photosynthetic protein, we contrast the description of such excitons provided by an exact basis set description, as opposed to a basis set with reduced vibrational dimensionality. Using a reduced analytical description of the full Hamiltonian, we show that in the presence of vibrational excitation both on electronically excited as well as unexcited sites, constructive interference between such basis states causes vibronic coupling between excitons to become progressively stronger with increasing quanta of vibrational excitation.

Selective functionalization at N-position of guanine in oligonucleotides via reductive amination.

Chemo- and site-specific modifications in oligonucleotides have wide applicability as mechanistic probes in chemical biology. However, methods that label specific sites in nucleic acids are scarce, especially for labeling DNA/RNA from biological or enzymatic sources rather than synthetic ones. Here we have employed a classical reaction, reductive amination, to selectively functionalize the N-amine of guanosine and 2'-deoxyguanosine monophosphate (GMP/dGMP).