Jastrow-Slater Wave Functions Research Articles

Multiple-Resonance Local Wave Functions for Accurate Excited States in Quantum Monte Carlo

We introduce a novel class of local multideterminant Jastrow-Slater wave functions for the efficient and accurate treatment of excited states in quantum Monte Carlo. The wave function is expanded as a linear combination of excitations built from multiple sets of localized orbitals that correspond to the bonding patterns of the different Lewis resonance structures of the molecule. We capitalize on the concept of orbital domains of local coupled-cluster methods, which is here applied to the active space to select the orbitals to correlate and construct the important transitions. The excitations are further grouped into classes, which are ordered in importance and can be systematically included in the Jastrow-Slater wave function to ensure a balanced description of all states of interest. We assess the performance of the proposed wave function in the calculation of vertical excitation energies and excited-state geometry optimization of retinal models whose π → π* state has a strong intramolecular charge-transfer character. We find that our multiresonance wave functions recover the reference values of the total energies of the ground and excited states with only a small number of excitations and that the same expansion can be flexibly used at very different geometries. Furthermore, significant computational saving can also be gained in the orbital optimization step by selectively mixing occupied and virtual orbitals based on spatial considerations without loss of accuracy on the excitation energy. Our multiresonance wave functions are therefore compact, accurate, and very promising for the calculation of multiple excited states of different character in large molecules.

Variational Quantum Monte Carlo with Inclusion of Orbital Correlations

Variational quantum Monte Carlo (VMC) method applied to interacting electron systems has played a pivotal role for the studies of electronic states of atoms, molecules and condensed matters. First, the many-body wave functions optimized by the VMC method provide good guiding functions in more accurate, diffusion quantum Monte Carlo (DMC) calculations for identical systems. Second, the VMC calculations themselves can give a good upper bound for the exact ground-state energy of many-electron systems when an appropriate form for the variational wave function is employed. In addition to a conventional form for the variational wave function that is expressed by the product of the Jastrow factor and the single Slater determinant, recent investigations have found that the expression in terms of many Slater determinants can provide a very accurate description of electronic states, especially for intrinsically multi-reference systems, which corresponds to the configuration interaction (CI) expansion method in conventional quantum chemistry. Although the CI method needs an extremely large number of expansion coefficients as variational parameters, the number of parameters can be reduced efficiently by using an idea of (molecular) orbital pair correlations. The purpose of the present paper is to examine the feasibility and usefulness of this idea within the framework of VMC method with the Jastrow–Slater wave function, where the ground state of a water molecule is investigated as a test case. In this study we rely on a variational wave function composed of a product of the Jastrow and Slater parts as 1⁄4 J S; ð1Þ

Orthogonal metals: The simplest non-Fermi liquids

We present a fractionalized metallic phase which is indistinguishable from the Fermi liquid in conductivity and thermodynamics, but is sharply distinct in one-electron properties, such as the electron spectral function. We dub this phase the ``orthogonal metal.'' The orthogonal metal and the transition to it from the Fermi liquid are naturally described using a slave-particle representation wherein the electron is expressed as a product of a fermion and a slave Ising spin. We emphasize that when the slave spins are disordered, the result is not a Mott insulator (as erroneously assumed in the prior literature), but rather the orthogonal metal. We construct prototypical ground-state wave functions for the orthogonal metal by modifying the Jastrow factor of Slater-Jastrow wave functions that describe ordinary Fermi liquids. We further demonstrate that the transition from the Fermi liquid to the orthogonal metal can, in some circumstances, provide a simple example of a continuous destruction of a Fermi surface with a critical Fermi surface appearing right at the critical point. We present exactly soluble models that realize an orthogonal metal phase, and the phase transition to the Fermi liquid. These models thus provide valuable solvable examples for phase transitions associated with the death of a Fermi surface.

Size-Extensive Wave Functions for Quantum Monte Carlo: A Linear Scaling Generalized Valence Bond Approach.

We propose a new class of multideterminantal Jastrow-Slater wave functions constructed with localized orbitals and designed to describe complex potential energy surfaces of molecular systems for use in quantum Monte Carlo (QMC). Inspired by the generalized valence bond formalism, we elaborate a coupling scheme between electron pairs which progressively includes new classes of excitations in the determinantal component of the wave function. In this scheme, we exploit the local nature of the orbitals to construct wave functions which have increasing complexity but scale linearly. The resulting wave functions are compact, can correlate all valence electrons, and are size extensive. We assess the performance of our wave functions in QMC calculations of the homolytic fragmentation of N-N, N-O, C-O, and C-N bonds, very common in molecules of biological interest. We find excellent agreement with experiments, and, even with the simplest forms of our wave functions, we satisfy chemical accuracy and obtain dissociation energies of equivalent quality to the CCSD(T) results computed with the large cc-pV5Z basis set.

Computing the energy of a water molecule using multideterminants: A simple, efficient algorithm

Quantum Monte Carlo (QMC) methods such as variational Monte Carlo and fixed node diffusion Monte Carlo depend heavily on the quality of the trial wave function. Although Slater-Jastrow wave functions are the most commonly used variational ansatz in electronic structure, more sophisticated wave functions are critical to ascertaining new physics. One such wave function is the multi-Slater-Jastrow wave function which consists of a Jastrow function multiplied by the sum of Slater determinants. In this paper we describe a method for working with these wave functions in QMC codes that is easy to implement, efficient both in computational speed as well as memory, and easily parallelized. The computational cost scales quadratically with particle number making this scaling no worse than the single determinant case and linear with the total number of excitations. Additionally, we implement this method and use it to compute the ground state energy of a water molecule.

Nonstochastic algorithms for Jastrow-Slater and correlator product state wave functions

Correlator product states (CPS) are a class of tensor network wavefunctions applicable to strongly correlated problems in arbitrary dimensions. Here, we present a method for optimizing and evaluating the energy of the CPS wavefunction that is non-variational but entirely deterministic. The fundamental assumption underlying our technique is that the CPS wavefunction is an exact eigenstate of the Hamiltonian, allowing the energy to be obtained approximately through a projection of the Schr\"odinger equation. The validity of this approximation is tested on two dimensional lattices for the spin-1/2 antiferromagnetic Heisenberg model, the spinless Hubbard model, and the full Hubbard model. In each of these models, the projected method reproduces the variational CPS energy to within 1%. For fermionic systems, we also demonstrate the incorporation of a Slater determinant reference into the ansatz, which allows CPS to act as a generalization of the Jastrow-Slater wavefunction.

A COMPOSITE FERMION APPROACH TO THE ULTRACOLD DILUTE FERMI GAS

It is argued that the recently observed Fermi liquids in strongly interacting ultracold Fermi gases are adiabatically connected to a projected Fermi gas. This conclusion is reached by constructing a set of Jastrow wavefunctions, following Tan's observations on the structure of the physical Hilbert space [Annals of Physics 323, 2952 (2008)]. The Jastrow projection merely implements the Bethe–Peierls condition on the BCS and Fermi gas wavefunctions. This procedure provides a simple picture of the emergence of Fermi polarons as composite fermions in the normal state of the highly polarized gas. It is also shown that the projected BCS wavefunction can be written as a condensate of pairs of composite fermions (or Fermi polarons). A Hamiltonian for the composite fermions is derived. Within a mean-field theory, it is shown that the ground state and excitations of this Hamiltonian are those of a non-interacting Fermi gas although they are described by Jastrow–Slater wavefunctions.

Relativistic quantum Monte Carlo method using zeroth-order regular approximation Hamiltonian

We propose a new relativistic treatment in the quantum Monte Carlo (QMC) technique using the zeroth-order regular approximation (ZORA) Hamiltonian. The novel ZORA local energy is derived, and its availability is examined with some variational Monte Carlo calculations. We optimize the wave functions variationally and evaluate the relativistic and correlation effects simultaneously. It is shown that our ZORA-QMC method with Jastrow-Slater wave functions can recover not only relativistic effects but also almost the same amount of electron correlations as the nonrelativistic QMC method can by evaluating the ionization potentials of the first row atoms, Li-Ne.

A JASTROW CORRELATION FACTOR FOR TWO-DIMENSIONAL PARABOLIC QUANTUM DOTS

One of the standard approaches to calculate the ground-state properties of strongly correlated electronic systems is to use a Jastrow–Slater wavefunction as a starting point. When considering confined electrons in a two-dimensional parabolic quantum dot, one chooses the Slater determinant to be the ground-state wavefunction of confined independent electrons and then determines the form of the Jastrow correlation factor in a way that incorporates accurately the spatial correlations of the system. One way to choose a quality Jastrow correlation factor is to consider the two-body problem and search the best possible yet simple approximative solution to such a problem. To achieve this goal, we consider the two-body problem of confined electrons interacting with a Coulomb repulsive potential in zero magnetic field and focus on their relative motion. Based on straightforward theoretical considerations, we suggest a simple two-body Jastrow correlation factor that optimizes very well the overall trial energy. We test the quality of the proposed Jastrow correlation factor by comparing the results to exact numerical diagonalization solutions.

Exact Jastrow-Slater wave function for the one-dimensional Luttinger model

We show that it is possible to describe the ground state of the Luttinger model in terms of a Jastrow-Slater wave function. Moreover, our findings reveal that one-particle excitations and their corresponding dynamics can be faithfully represented only when a Jastrow factor of a similar form is applied to a coherent superposition of many Slater determinants. We discuss the possible relevance of this approach for the theoretical description of photoemission spectra in higher dimensionality, where the present wave function can be straightforwardly generalized and can be used as a variational ansatz, which is exact for the one-dimensional (1D) Luttinger model.

Variational Monte Carlo calculation of the nematic state of the two-dimensional electron gas in a magnetic field

We use a Jastrow-Slater wave function with an elliptical Fermi sea to describe the nematic state of the two-dimensional electron gas in a magnetic field and the Monte Carlo method to calculate a variational energy upper bound. These energy upper bounds are compared with other upper bounds describing stripe-ordered ground states, which are obtained from optimized Hartree-Fock calculations, and with those which correspond to an isotropic ground state. Our findings support the conclusions drawn in our previous study, where the Fermi-hypernetted chain approximation was used instead of the Monte Carlo method. Namely, the nematic state becomes energetically favorable relative to the stripe-ordered Wigner crystal phase for the second excited Landau level and below a critical value of the layer ``thickness'' parameter, which is very close to its value in the actual materials.

Full optimization of Jastrow–Slater wave functions with application to the first-row atoms and homonuclear diatomic molecules

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. We extend the method to optimize the exponents of the basis functions, simultaneously with all the other parameters, namely, the Jastrow, configuration state function, and orbital parameters. We show that the linear optimization method can be thought of as a so-called augmented Hessian approach, which helps explain the robustness of the method and permits us to extend it to minimize a linear combination of the energy and the energy variance. We apply the linear optimization method to obtain the complete ground-state potential energy curve of the C(2) molecule up to the dissociation limit and discuss size consistency and broken spin-symmetry issues in quantum Monte Carlo calculations. We perform calculations for the first-row atoms and homonuclear diatomic molecules with fully optimized Jastrow-Slater wave functions, and we demonstrate that molecular well depths can be obtained with near chemical accuracy quite systematically at the diffusion Monte Carlo level for these systems.

Quantum Monte Carlo calculations of the potential energy curve of the helium dimer

We report results of two quantum Monte Carlo methods -- variational Monte Carlo and diffusion Monte Carlo -- on the potential energy curve of the helium dimer. In contrast to previous quantum Monte Carlo calculations on this system, we have employed trial wave functions of the Slater-Jastrow form and used the fixed node approximation for the fermion nodal surface. We find both methods to be in excellent agreement with the best theoretical results at short range. In addition, the diffusion Monte Carlo results give very good agreement across the whole potential energy curve, while the Slater-Jastrow wave function fails to bind the dimer at all.

Zero-variance zero-bias quantum Monte Carlo estimators of the spherically and system-averaged pair density

We construct improved quantum Monte Carlo estimators for the spherically and system-averaged electron pair density (i.e., the probability density of finding two electrons separated by a relative distance u), also known as the spherically averaged electron position intracule density I(u), using the general zero-variance zero-bias principle for observables, introduced by Assaraf and Caffarel. The calculation of I(u) is made vastly more efficient by replacing the average of the local delta-function operator by the average of a smooth nonlocal operator that has several orders of magnitude smaller variance. These new estimators also reduce the systematic error (or bias) of the intracule density due to the approximate trial wave function. Used in combination with the optimization of an increasing number of parameters in trial Jastrow-Slater wave functions, they allow one to obtain well converged correlated intracule densities for atoms and molecules. These ideas can be applied to calculating any pair-correlation function in classical or quantum Monte Carlo calculations.

Energies of the first row atoms from quantum Monte Carlo

All-electron variational and diffusion quantum Monte Carlo calculations of the ground state energies of the first row atoms (from Li to Ne) are reported. The authors use trial wave functions of four types: single-determinant Slater-Jastrow wave functions, multideterminant Slater-Jastrow wave functions, single-determinant Slater-Jastrow wave functions with backflow transformations, and multideterminant Slater-Jastrow wave functions with backflow transformations. At the diffusion quantum Monte Carlo level and using their multideterminant Slater-Jastrow wave functions with backflow transformations, they recover 99% or more of the correlation energies for Li, Be, B, C, N, and Ne, 97% for O, and 98% for F.

Generalized description of few-electron quantum dots at zero and nonzero magneticfields

We introduce a generalized ground state variational wavefunction for parabolically confinedtwo-dimensional quantum dots that equally applies to both cases of weak (or zero) andstrong magnetic field. The wavefunction has a Laughlin-like form in the limit of infinitemagnetic field, but transforms into a Jastrow–Slater wavefunction at zero magnetic field.At intermediate magnetic fields (where a fraction of electrons is spin-reversed) itresembles Halperin’s spin-reversed wavefunction for the fractional quantum Halleffect. The properties of this variational wavefunction are illustrated for the caseof two-dimensional quantum dot helium (a system of two interacting electronsin a parabolic confinement potential) where we find the description to be anexcellent representation of the true ground state for the whole range of magneticfields.

Quantum Monte Carlo calculations of the dissociation energy of the water dimer

We report diffusion quantum Monte Carlo (DMC) calculations of the equilibrium dissociation energy D(e) of the water dimer. The dissociation energy measured experimentally, D(0), can be estimated from D(e) by adding a correction for vibrational effects. Using the measured dissociation energy and the modern value of the vibrational energy Mas et al., [J. Chem. Phys. 113, 6687 (2000)] leads to D(e)=5.00+/-0.7 kcal mol(-1), although the result Curtiss et al., [J. Chem. Phys. 71, 2703 (1979)] D(e)=5.44+/-0.7 kcal mol(-1), which uses an earlier estimate of the vibrational energy, has been widely quoted. High-level coupled cluster calculations Klopper et al., [Phys. Chem. Chem. Phys. 2, 2227 (2000)] have yielded D(e)=5.02+/-0.05 kcal mol(-1). In an attempt to shed new light on this old problem, we have performed all-electron DMC calculations on the water monomer and dimer using Slater-Jastrow wave functions with both Hartree-Fock approximation (HF) and B3LYP density functional theory single-particle orbitals. We obtain equilibrium dissociation energies for the dimer of 5.02+/-0.18 kcal mol(-1) (HF orbitals) and 5.21+/-0.18 kcal mol(-1) (B3LYP orbitals), in good agreement with the coupled cluster results.

Quantum Monte Carlo calculations of the dissociation energies of three-electron hemibonded radical cationic dimers

We report variational and diffusion quantum Monte Carlo (VMC and DMC) calculations of the dissociation energies of the three-electron hemibonded radical cationic dimers of He, NH3, H2O, HF, and Ne. These systems are particularly difficult for standard density-functional methods such as the local-density approximation and the generalized gradient approximation. We have performed both all-electron (AE) and pseudopotential (PP) calculations using Slater-Jastrow wave functions with Hartree-Fock single-particle orbitals. Our results are in good agreement with coupled-cluster CCSD(T) calculations. We have also studied the relative stability of the hemibonded and hydrogen-bonded water radical dimer isomers. Our calculations indicate that the latter isomer is more stable, in agreement with post-Hartree-Fock methods. The excellent agreement between our AE and PP results demonstrates the high quality of the PPs used within our VMC and DMC calculations.

All-electron quantum Monte Carlo calculations for the noble gas atoms He to Xe

We report all-electron variational and diffusion quantum Monte Carlo (VMC and DMC) calculations for the noble gas atoms He, Ne, Ar, Kr, and Xe. The calculations were performed using Slater-Jastrow wave functions with Hartree-Fock single-particle orbitals. The quality of both the optimized Jastrow factors and the nodal surfaces of the wave functions declines with increasing atomic number Z, but the DMC calculations are tractable and well behaved in all cases. We discuss the scaling of the computational cost of DMC calculations with Z.

Optimized Jastrow-Slater wave functions for ground and excited states: application to the lowest states of ethene.

A quantum Monte Carlo method is presented for determining multideterminantal Jastrow-Slater wave functions for which the energy is stationary with respect to the simultaneous optimization of orbitals and configuration interaction coefficients. The approach is within the framework of the so-called energy fluctuation potential method which minimizes the energy in an iterative fashion based on Monte Carlo sampling and a fitting of the local energy fluctuations. The optimization of the orbitals is combined with the optimization of the configuration interaction coefficients through the use of additional single excitations to a set of external orbitals. A new set of orbitals is then obtained from the natural orbitals of this enlarged configuration interaction expansion. For excited states, the approach is extended to treat the average of several states within the same irreducible representation of the pointgroup of the molecule. The relationship of our optimization method with the stochastic reconfiguration technique by Sorella et al. is examined. Finally, the performance of our approach is illustrated with the lowest states of ethene, in particular with the difficult case of the 1(1)B(1u) state.