Previous calculations on model systems for the cooperative binding of two NO2 molecules to carbon nanotubes using density functional theory and second order Moller-Plesset perturbation theory gave results differing by 30 kcal/mol. Quantum Monte Carlo calculations are performed to study the role of electronic correlations in these systems and resolve the discrepancy between these previous calculations. Compared to QMC binding energies, MP2 and LDA are shown to overbind, while B3LYP and BPW91 underbind.

Over the past two decades, continuum quantum Monte Carlo (QMC) has proved to be an invaluable tool for predicting of the properties of matter from fundamental principles. By solving the Schrödinger equation through a stochastic projection, it achieves the greatest accuracy and reliability of methods available for physical systems containing more than a few quantum particles. QMC enjoys scaling favorable to quantum chemical methods, with a computational effort which grows with the second or third power of system size.

We pursue the development and application of the recently introduced linear optimization method for determining the optimal linear and nonlinear parameters of Jastrow-Slater wave functions in a variational Monte Carlo framework. In this approach, the optimal parameters are found iteratively by diagonalizing the Hamiltonian matrix in the space spanned by the wave function and its first-order derivatives, making use of a strong zero-variance principle.

Diffusion Monte Carlo (DMC) calculations are performed on the monocyclic and bicyclic forms of m -benzyne, which are the equilibrium structures at the CCSD(T) and CCSD levels of coupled cluster theory. We employed multiconfiguration self-consistent field trial wave functions which are constructed from a carefully selected eight-electrons-in-eight-orbitals complete active space [CAS(8,8)], with configuration state function coefficients that are reoptimized in the presence of a Jastrow factor.

We argue that Coulomb blockade phenomena are a useful probe of the crossover to strong correlation in quantum dots. Through calculations at low density using variational and diffusion quantum Monte Carlo (up to rs ∼55), we find that the addition energy shows a clear progression from features associated with shell structure to those caused by commensurability of a Wigner crystal. This crossover (which occurs near rs ∼20 for spin-polarized electrons) is, then, a signature of interaction-driven localization.