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Register a new userQuantum Proton Effects from Density Matrix Renormalization Group Calculations
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We recently introduced [J. Chem. Phys. 152 2020, 204103] the nuclear-electronic all-particle density matrix renormalization group method (NEAP-DMRG) to solve the molecular Schr{o}dinger equation, based on a stochastically optimized orbital basis, without invoking the Born-Oppenheimer approximation. In this work, we combine the DMRG with nuclear-electronic Hartree-Fock (NEHF-DMRG), treating nuclei and electrons on the same footing. Inter- and intra-species correlations are described within the DMRG without truncating the excitation degree of the full configuration interaction wave function. We extend the concept of orbital entanglement and mutual information to nuclear-electronic wave functions and demonstrate that they are reliable metrics to detect strong correlation effects. We apply NEHF-DMRG to the HeHHe$^+$ molecular ion, to obtain accurate proton densities, ground-state total energies, and vibrational transition frequencies by comparison with state-of-the-art data obtained with grid-based approaches and modern configuration interaction methods. For HCN, we improve on the accuracy of the latter approaches with respect to both ground-state absolute energy and proton density which is a major challenge for multi-reference nuclear-electronic state-of-the-art methods.
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We introduce the Nuclear Electronic All-Particle Density Matrix Renormalization Group (NEAP-DMRG) method for solving the time-independent Schrodinger equation simultaneously for electrons and other quantum species. In contrast to already existing multicomponent approaches, in this work we construct from the outset a multi-reference trial wave function with stochastically optimized non-orthogonal Gaussian orbitals. By iterative refining of the Gaussians positions and widths, we obtain a compact multi-reference expansion for the multicomponent wave function. We extend the DMRG algorithm to multicomponent wave functions to take into account inter- and intra-species correlation effects. The efficient parametrization of the total wave function as a matrix product state allows NEAP-DMRG to accurately approximate full configuration interaction energies of molecular systems with more than three nuclei and twelve particles in total, which is currently a major challenge for other multicomponent approaches. We present NEAP-DMRG results for two few-body systems, i.e., H$_2$ and H$_3^+$, and one larger system, namely BH$_3$
We present a matrix-product state (MPS)-based quadratically convergent density-matrix renormalization group self-consistent-field (DMRG-SCF) approach. Following a proposal by Werner and Knowles (JCP 82, 5053, (1985)), our DMRG-SCF algorithm is based on a direct minimization of an energy expression which is correct to second-order with respect to changes in the molecular orbital basis. We exploit a simultaneous optimization of the MPS wave function and molecular orbitals in order to achieve quadratic convergence. In contrast to previously reported (augmented Hessian) Newton-Raphson and super-configuration-interaction algorithms for DMRG-SCF, energy convergence beyond a quadratic scaling is possible in our ansatz. Discarding the set of redundant active-active orbital rotations, the DMRG-SCF energy converges typically within two to four cycles of the self-consistent procedure
In this work, we simulate the electron dynamics in molecular systems with the Time-Dependent Density Matrix Renormalization Group (TD-DMRG) algorithm. We leverage the generality of the so-called tangent-space TD-DMRG formulation and design a computational framework in which the dynamics is driven by the exact non-relativistic electronic Hamiltonian. We show that, by parametrizing the wave function as a matrix product state, we can accurately simulate the dynamics of systems including up to 20 electrons and 32 orbitals. We apply the TD-DMRG algorithm to three problems that are hardly targeted by time-independent methods: the calculation of molecular (hyper)polarizabilities, the simulation of electronic absorption spectra, and the study of ultrafast ionization dynamics.
We present the first implementation of a density matrix renormalization group algorithm embedded in an environment described by density functional theory. The frozen density embedding scheme is used with a freeze-and-thaw strategy for a self-consistent polarization of the orbital-optimized wavefunction and the environmental densities with respect to each other.
Variational approaches for the calculation of vibrational wave functions and energies are a natural route to obtain highly accurate results with controllable errors. However, the unfavorable scaling and the resulting high computational cost of standard variational approaches limit their application to small molecules with only few vibrational modes. Here, we demonstrate how the density matrix renormalization group (DMRG) can be exploited to optimize vibrational wave functions (vDMRG) expressed as matrix product states. We study the convergence of these calculations with respect to the size of the local basis of each mode, the number of renormalized block states, and the number of DMRG sweeps required. We demonstrate the high accuracy achieved by vDMRG for small molecules that were intensively studied in the literature. We then proceed to show that the complete fingerprint region of the sarcosyn-glycin dipeptide can be calculated with vDMRG.
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