Rene Derian

Quantum Monte Carlo Methods Describe Noncovalent Interactions with Subchemical Accuracy

An accurate description of noncovalent interaction energies is one of the most challenging tasks in computational chemistry. To date, nonempirical CCSD(T)/CBS has been used as a benchmark reference. However, its practical use is limited due to the rapid growth of its computational cost with the system complexity. Here, we show that the fixed-node diffusion Monte Carlo (FN-DMC) method with a more favorable scaling is capable of reaching the CCSD(T)/CBS within subchemical accuracy (<0.1 kcal/mol) on a testing set of six small noncovalent complexes including the water dimer. In benzene/water, benzene/methane, and the T-shape benzene dimer, FN-DMC provides interaction energies that agree within 0.25 kcal/mol with the best available CCSD(T)/CBS estimates. The demonstrated predictive power of FN-DMC therefore provides new opportunities for studies of the vast and important class of medium/large noncovalent complexes.

Ground and excited electronic states of azobenzene: A quantum Monte Carlo study

Large-scale quantum Monte Carlo (QMC) calculations of ground and excited singlet states of both conformers of azobenzene are presented. Remarkable accuracy is achieved by combining medium accuracy quantum chemistry methods with QMC. The results not only reproduce measured values with chemical accuracy but the accuracy is sufficient to identify part of experimental results which appear to be biased. Novel analysis of nodal surface structure yields new insights and control over their convergence, providing boost to the chemical accuracy electronic structure methods of large molecular systems.

Product Wave Function Renormalization Group: Construction from the Matrix Product Point of View

We present a construction of a matrix product state (MPS) that approximates the largest-eigenvalue eigenvector of a transfer matrix T of a two-dimensional classical lattice model. A state vector created from the upper or the lower half of a finite size cluster approximates the largest-eigenvalue eigenvector. Decomposition of this state vector into the MPS gives a way of extending the MPS recursively. The extension process is a special case of the product wave function renormalization group (PWFRG) method, that accelerates the numerical calculation of the infinite system density matrix renormalization group (DMRG) method. As a result, we successfully give the physical interpretation of the PWFRG method, and obtain its appropriate initial condition.

Modulation of Local Magnetization in Two-Dimensional Axial-Next-Nearest-Neighbor Ising Model

The axial next-nearest-neighbor Ising model is studied in two dimensions at finite temperature using the density matrix renormalization group. The model exhibits phase transition of the second-order between the antiphase in low temperature and the modulated phase in high temperature. Observing the domain wall free energy, we confirm that the modulation period in high-temperature side is well explained by the free-fermion picture.

Strain control of vibrational properties of few layer phosphorene

Using density functional theory techniques, we study lattice vibrational Raman and infrared modes in strained few-layer phosphorene. We find very significant frequency shifts, up to ≈ 100 cm−1 in the applied strain range of ±6%, of the Raman activities in both high- and low-frequency region and infrared activities in the low-frequency region. The type of applied strain, that is, armchair and zigzag, selectively affects specific vibrational modes. Combined with high spatial-resolution Raman/infrared scattering experiments, our calculated results can aid understanding of the complicated inhomogeneous strain distributions in few-layer phosphorene or manufacturing of materials with desired electronic properties via strain or layer engineering.

Charged vanadium-benzene multidecker clusters: DFT and quantum Monte Carlo study

Using explicitly correlated fixed-node quantum Monte Carlo and density functional theory (DFT) methods, we study electronic properties, ground-state multiplets, ionization potentials, electron affinities, and low-energy fragmentation channels of charged half-sandwich and multidecker vanadium-benzene systems with up to 3 vanadium atoms, including both anions and cations. It is shown that, particularly in anions, electronic correlations play a crucial role; these effects are not systematically captured with any commonly used DFT functionals such as gradient corrected, hybrids, and range-separated hybrids. On the other hand, tightly bound cations can be described qualitatively by DFT. A comparison of DFT and quantum Monte Carlo provides an in-depth understanding of the electronic structure and properties of these correlated systems. The calculations also serve as a benchmark study of 3d molecular anions that require a balanced many-body description of correlations at both short- and long-range distances.