Connection between the observable and centroid structural properties of a quantum fluid: application to liquid para-hydrogen

It is shown that the discrepancy between path integral Monte Carlo [M. Zoppi et al., Phys. Rev. B 65, 092204 (2002)] and path integral centroid molecular dynamics [F. J. Bermejo et al., Phys. Rev. Lett. 84, 5359 (2000)] calculations of the static structure factor of liquid para-hydrogen can be explained based on a deconvolution equation connecting centroid and physical radial distribution functions. An explicit expression for the kernel of the deconvolution equation has been obtained using functional derivative techniques. In the superposition approximation, this kernel is given by the functional derivative of the effective potential with respect to the pairwise classical potential. Results of path integral Monte Carlo calculations for the radial distribution function and the static structure factor of liquid para-hydrogen are presented.     

Hybrid quantum/classical path integral approach for simulation of hydrogen transfer reactions in enzymes

A hybrid quantum/classical path integral Monte Carlo (QC-PIMC) method for calculating the quantum free energy barrier for hydrogen transfer reactions in condensed phases is presented. In this approach, the classical potential of mean force along a collective reaction coordinate is calculated using umbrella sampling techniques in conjunction with molecular dynamics trajectories propagated according to a mapping potential. The quantum contribution is determined for each configuration along the classical trajectory with path integral Monte Carlo calculations in which the beads move according to an effective mapping potential. This type of path integral calculation does not utilize the centroid constraint and can lead to more efficient sampling of the relevant region of conformational space than free-particle path integral sampling. The QC-PIMC method is computationally practical for large systems because the path integral sampling for the quantum nuclei is performed separately from the classical molecular dynamics sampling of the entire system. The utility of the QC-PIMC method is illustrated by an application to hydride transfer in the enzyme dihydrofolate reductase. A comparison of this method to the quantized classical path and grid-based methods for this system is presented.     

Nuclear quantum effect on the hydrogen-bonded structure of guanine�Ccytosine pair

The structure of Watson?CCrick type guanine?Ccytosine (G?CC) base pair has been studied by classical hybrid Monte Carlo (HMC) and quantum path integral hybrid Monte Carlo (PIHMC) simulations on the semiempirical PM6 potential energy surface. For the three NH?X hydrogen-bonded moieties, the intramolecular NH bonds are found systematically longer while the H?X distance shorter in the PIHMC simulation than in the HMC simulation. We found that the hydrogen bonded length N?X correlates with the H?X distance, but not with the NH distance. A correlation is also between the neighboring hydrogen bonds in the G?CC base pair.     

Forward--backward semiclassical dynamics with information-guided noise reduction for a molecule in solution

The forward--backward semiclassical dynamics (FBSD) methodology is used to obtain expressions for time correlation functions of a system (atom or molecule) in solution. We use information-guided noise reduction (IGNoR) [Makri, N. Chem. Phys. Lett. 2004, 400, 446] to minimize the statistical error associated with the Monte Carlo integration of oscillatory functions. This is possible by reformulating the correlation function in terms of an oscillatory solvent-dependent contribution whose integral can be obtained analytically and a slowly varying function obtained via a grid-based iterative evaluation of solute properties. Knowledge of the exact integral of the oscillatory function, combined with correlated statistics, leads to partial cancellation of the Monte Carlo error. Application on a one-dimensional solute-solvent model shows a substantial improvement of convergence in the IGNoR-enhanced FBSD correlation function for a fixed number of Monte Carlo samples. The reduction of statistical error achieved by using the IGNoR methodology becomes more significant as the number of solvent particles increases.     

Electron pair localization function: a practical tool to visualize electron localization in molecules from quantum Monte Carlo data

In this work we introduce an electron localization function describing the pairing of electrons in a molecular system. This function, called "electron pair localization function," is constructed to be particularly simple to evaluate within a quantum Monte Carlo framework. Two major advantages of this function are the following: (i) the simplicity and generality of its definition; and (ii) the possibility of calculating it with quantum Monte Carlo at various levels of accuracy (Hartree-Fock, multiconfigurational wave functions, valence bond, density functional theory, variational Monte Carlo with explicitly correlated trial wave functions, fixed-node diffusion Monte Carlo, etc). A number of applications of the electron pair localization function to simple atomic and molecular systems are presented and systematic comparisons with the more standard electron localization function of Becke and Edgecombe are done. Results illustrate that the electron pair localization function is a simple and practical tool for visualizing electronic localization in molecular systems.     

Solution of the Percus-Yevick equation for hard disks

The authors solve the Percus-Yevick equation in two dimensions by reducing it to a set of simple integral equations. They numerically obtain both the pair correlation function and the equation of state for a hard disk fluid and find good agreement with available Monte Carlo results. The present method of resolution may be generalized to any even dimension.     

Path integral ground state with a fourth-order propagator: application to condensed helium

Ground state properties of condensed helium are calculated using the path integral ground state (PIGS) method. A fourth-order approximation is used as short (imaginary) time propagator. We compare our results with those obtained with other quantum Monte Carlo (QMC) techniques and different propagators. For this particular application, we find that the fourth-order propagator performs comparably to the pair product approximation, and is far superior to the primitive approximation. Results obtained for the equation of state of condensed helium show that PIGS compares favorably to other QMC methods traditionally utilized for this type of calculation.     

Quantum features of a barely bound molecular dopant: Cs2(3Σu) in bosonic helium droplets of variable size

We present in this work the study of small (4)He(N)-Cs(2)((3)Σ(u)) aggregates (2 ≤ N ≤ 30) through combined variational, diffusion Monte Carlo (DMC), and path integral Monte Carlo (PIMC) calculations. The full surface is modeled as an addition of He-Cs(2) interactions and He-He potentials. Given the negligible strength and large range of the He-Cs(2) interaction as compared with the one for He-He, a propensity of the helium atoms to pack themselves together, leaving outside the molecular dopant is to be expected. DMC calculations determine the onset of helium gathering at N = 3. To analyze energetic and structural properties as a function of N, PIMC calculations with no bosonic exchange, i.e., Boltzmann statistics, at low temperatures are carried out. At T = 0.1 K, although acceptable one-particle He-Cs(2) distributions are obtained, two-particle He-He distributions are not well described, indicating that the proper symmetry should be taken into account. PIMC distributions at T = 1 K already compare well with DMC ones and show minor exchange effects, although binding energies are still far from having converged in terms of the number of quantum beads. As N increases, the He-He PIMC pair correlation function shows a clear tendency to coincide with the experimental boson-liquid helium one at that temperature. It supports the picture of a helium droplet which carries the molecular impurity on its surface, as found earlier for other triplet dimers.     

A variational principle in Wigner phase-space with applications to statistical mechanics

We consider the Dirac-Frenkel variational principle in Wigner phase-space and apply it to the Wigner-Liouville equation for both imaginary and real time dynamical problems. The variational principle allows us to deduce the optimal time-evolution of the parameter-dependent Wigner distribution. It is shown that the variational principle can be formulated alternatively as a "principle of least action." Several low-dimensional problems are considered. In imaginary time, high-temperature classical distributions are "cooled" to arrive at low-temperature quantum Wigner distributions whereas in real time, the coherent dynamics of a particle in a double well is considered. Especially appealing is the relative ease at which Feynman's path integral centroid variable can be incorporated as a variational parameter. This is done by splitting the high-temperature Boltzmann distribution into exact local centroid constrained distributions, which are thereafter cooled using the variational principle. The local distributions are sampled by Metropolis Monte Carlo by performing a random walk in the centroid variable. The combination of a Monte Carlo and a variational procedure enables the study of quantum effects in low-temperature many-body systems, via a method that can be systematically improved.     

Triplet correlations in the quantum hard-sphere fluid

A study of three-particle correlations in the quantum hard-sphere fluid far from exchange is presented. The three types of triplet correlations in a monatomic quantum fluid (instantaneous, linear response, and centroids) are analyzed by utilizing (a) the density derivatives of the corresponding quantum pair radial correlation functions, (b) closures for triplet functions, and (c) path-integral Monte Carlo (PIMC) simulations that have concentrated on the fixing of equilateral and isosceles correlations. For the sake of comparison, the classical hard-sphere fluid is also studied with tools (a) and (b) and Monte Carlo (MC) simulations. The relative usefulness of density derivatives combined with closures is discussed in light of the PIMC and MC results. The exact PIMC correlations between quantum triplets show features that resemble those known to occur at the pair level, such as the close proximity between the instantaneous and the three-particle linear response, the much more pronounced features in centroid triplet structures, and the same global patterns with changes in density and temperature such as the outward shifts of the structures with decreasing temperature and density.     

Spatial delocalization in para-H2 clusters

We applied the quantum path integral Monte Carlo method for the study of (para-H)N (N = 5-33) clusters at T = 2 K, exploring static and dynamic order, which originates from the effects of zero-point energy, kinetic energy, and thermal fluctuations in quantum clusters. Information on dynamic structure was inferred from the asymptotic tails of the cage correlation function calculated from the centroid Monte Carlo trajectory. The centroid cage correlation function decays to zero for large clusters (N = 15-33), manifesting the interchange of molecules between different solvation shells, with statistically diminishing back interchange. Further evidence for the floppiness of para-hydrogen clusters emerges from the Monte Carlo evolution of the centroid of a tagged molecule, which exhibits significant changes in the list of its first and second solvation shells due to the interchange of molecules between these shells.     

An integral equation theory for inhomogeneous molecular fluids: the reference interaction site model approach

An integral equation theory which is applicable to inhomogeneous molecular liquids is proposed. The "inhomogeneous reference interaction site model (RISM)" equation derived here is a natural extension of the RISM equation to inhomogeneous systems. This theory makes it possible to calculate the pair correlation function between two molecules which are located at different density regions. We also propose approximations concerning the closure relation and the intramolecular susceptibility of inhomogeneous molecular liquids. As a preliminary application of the theory, the hydration structure around an ion is investigated. Lithium, sodium, and potassium cations are chosen as the solute. Using the Percus trick, the local density of solvent around an ion is expressed in terms of the solute-solvent pair correlation function calculated from the RISM theory. We then analyze the hydration structure around an ion through the triplet correlation function which is defined with the inhomogeneous pair correlation function and the local density of the solvent. The results of the triplet correlation functions for cations indicate that the thermal fluctuation of the hydration shell is closely related to the size of the solute ion. The triplet correlation function from the present theory is also compared with that from the Kirkwood superposition approximation, which substitutes the inhomogeneous pair correlation by the homogeneous one. For the lithium ion, the behavior of the triplet correlation functions from the present theory shows marked differences from the one calculated within the Kirkwood approximation.     

Path integral Monte Carlo approach for weakly bound van der Waals complexes with rotations: algorithm and benchmark calculations

A path integral Monte Carlo technique suitable for the treatment of doped helium clusters with inclusion of the rotational degrees of freedom of the dopant is introduced. The extrapolation of the results to the limit of infinite Trotter number is discussed in detail. Benchmark calculations for small weakly bound (4)He(N)--OCS clusters are presented. The Monte Carlo results are compared with those of basis set calculations for the He--OCS dimer. A technique to analyze the orientational imaginary time correlation function is suggested. It allows one to obtain information regarding the effective rotational constant for a doped helium cluster based on a model for the rotational Hamiltonian. The renormalization of the effective rotational constant for (4)He(N)--OCS clusters derived from the orientational imaginary time correlation function is in good agreement with experimental results.     

Efficient estimators for quantum instanton evaluation of the kinetic isotope effects: application to the intramolecular hydrogen transfer in pentadiene

The quantum instanton approximation is used to compute kinetic isotope effects for intramolecular hydrogen transfer in cis-1,3-pentadiene. Due to the importance of skeleton motions, this system with 13 atoms is a simple prototype for hydrogen transfer in enzymatic reactions. The calculation is carried out using thermodynamic integration with respect to the mass of the isotopes and a path integral Monte Carlo evaluation of relevant thermodynamic quantities. Efficient "virial" estimators are derived for the logarithmic derivatives of the partition function and the delta-delta correlation functions. These estimators require significantly fewer Monte Carlo samples since their statistical error does not increase with the number of discrete time slices in the path integral. The calculation treats all 39 degrees of freedom quantum mechanically and uses an empirical valence bond potential based on a molecular mechanics force field.     

Monte Carlo approach to the decay rate of a metastable system with an arbitrarily shaped barrier

A path integral Monte Carlo method based on the fast-Fourier transform technique combined with the important sampling method is proposed to calculate the decay rate of a metastable quantum system with an arbitrary shape of a potential barrier. The contribution of all fluctuation actions is included which can be used to check the accuracy of the usual steepest-descent approximation, namely, the perturbation expansion of potential. The analytical approximation is found to produce the decay rate of a particle in a cubic potential being about 20% larger than the Monte Carlo data at the crossover temperature. This disagreement increases with increasing complexity of the potential shape. We also demonstrate via Langevin simulation that the postsaddle potential influences strongly upon the classical escape rate.     

Electrostatic exchange-correlation charge density in Be and Ne: quantal density functional theoretic analysis

Using classical electrostatics, the total effective integrated charge-density function is calculated for Be and Ne using the multiplicative potentials derived from (1) Hartree and (2) Hartree–Fock approximation to quantal density functional theory (3)exchange-only optimized effective potential and (4) Kohn–Sham exchange-correlation potential using the quantum Monte Carlo density. The evolution of effective integrated charge-density function for these atoms is examined as the electron correlation is built up stepwise from its absence to the stage of its near complete presence. These results provide a deeper understanding of the Kohn–Sham exchange-correlation potential in terms the correspondingly defined integrated charge-density functions based on the Poisson equation. This paper is dedicated to Professor Karl Jug on the occasion of his 65th Birthday     

Phase changes in selected Lennard-Jones X13-nYn clusters

Detailed studies of the thermodynamic properties of selected binary Lennard-Jones clusters of the type X13-nYn (where n=1, 2, 3) are presented. The total energy, heat capacity, and first derivative of the heat capacity as a function of temperature are calculated by using the classical and path integral Monte Carlo methods combined with the parallel tempering technique. A modification in the phase change phenomena from the presence of impurity atoms and quantum effects is investigated.     

Including quantum subsystem character within classical equilibrium simulations

A mixed quantum/classical density matrix approximation is derived. The density matrix makes use of quantum subsystem vibrational wave functions. The diagonal of the density matrix can be used as an equilibrium distribution in Monte Carlo simulations. The approximate distribution compares well with the path integral distribution for a model system. Since it includes quantum subsystem information, it performs much better than the quadratic Feynman-Hibbs distribution. These types of distributions can aid in including quantum vibrational information in otherwise classical simulations.     

The phase diagram of water from quantum simulations

The phase diagram of water has been calculated from the TIP4PQ/2005 model, an empirical rigid non-polarisable model. The path integral Monte Carlo technique was used, permitting the incorporation of nuclear quantum effects. The coexistence lines were traced out using the Gibbs-Duhem integration method, once having calculated the free energies of the liquid and solid phases in the quantum limit, which were obtained via thermodynamic integration from the classical value by scaling the mass of the water molecule. The resulting phase diagram is qualitatively correct, being displaced to lower temperatures by 15-20 K. It is found that the influence of nuclear quantum effects is correlated to the tetrahedral order parameter.