SEARCH · Searcharxiv

Results for “physics.chem-ph”

Search indexed arXiv papers on artificial intelligence, large language models, computer vision and robotics. Read source abstracts and follow links to arXiv.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,207 records · Page 67Linked to original sources

arXiv2013

Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions

We present an investigation into the use of an explicitly correlated plane wave basis for periodic wavefunction expansions at the level of second-order Møller-Plesset perturbation theory (MP2). The convergence of the electronic correlation energy with respect to the one-electron basis set is investigated and compared to conventional MP2 theory in a finite homogeneous electron gas model. In addition to the widely used Slater-type geminal correlation factor, we also derive and investigate a novel correlation factor that we term Yukawa-Coulomb. The Yukawa-Coulomb correlation factor is motivated by analytic results for two electrons in a box and allows for a further improved convergence of the correlation energies with respect to the employed basis set. We find the combination of the infinitely delocalized plane waves and local short-ranged geminals provides a complementary, and rapidly convergent basis for the description of periodic wavefunctions. We hope that this approach will expand the scope of discrete wavefunction expansions in periodic systems.

physics.comp-ph↗

arXiv2013

The phase diagram of ice: a quasi-harmonic study based on a flexible water model

The phase diagram of ice is studied by a quasi-harmonic approximation. The free energy of all experimentally known ice phases has been calculated with the flexible q-TIP4P/F model of water. The only exception is the high pressure ice X, in which the presence of symmetric O-H-O bonds prevents its modeling with this empirical interatomic potential. The simplicity of our approach allows us to study ice phases at state points of the T-P plane that have been omitted in previous simulations using free energy methods based on thermodynamic integration. The effect in the phase diagram of averaging the proton disorder that appears in several ice phases has been studied. It is found particularly relevant for ice III, at least for cell sizes typically used in phase coexistence simulations. New insight into the capability of the employed water model to describe the coexistence of ice phases is presented. We find that the H-ordered ices IX and XIV, as well as the H-disordered ice XII, are particularly stable for this water model. This fact disagrees with experimental data. The unexpected large stability of ice IX is a property related to the TIP4P-character of the water model. Only after omission of these three stable ice phases, the calculated phase diagram becomes in reasonable qualitative agreement to the experimental one in the T-P region corresponding to ice Ih, II, III, V, and VI. The calculation of the phase diagram in the quantum and classical limits shows that the most important quantum effect is the stabilization of ice II due to its lower zero-point energy when compared to that one of ices Ih, III, and V.

physics.chem-ph↗

arXiv2013

The quest for self-consistency in hydrogen-bond definitions

In the last decades several hydrogen-bond definitions were proposed by classical computer simulations. Aiming at validating their self-consistency on a wide range of conditions, here we present a comparative study of six among the most common hydrogen-bond definitions for temperatures ranging from 220K to 400K and six classical water models. Our results show that, in the interval of temperatures investigated, a generally weak agreement among definitions is present. Moreover, cutoff choice for geometrically based definitions depends on both temperature and water model. As such, analysis of the same water model at different temperatures as well as different water models at the same temperature would require the development of specific cutoff values. Interestingly, large discrepancies were found between two hydrogen-bond definitions which were recently introduced to improve on more conventional methods. Our results anticipate that a more universal way to characterize hydrogen-bonds in classical molecular systems is needed.

physics.chem-ph↗

arXiv2013

Exploring covalently bonded diamondoid particles with valence photoelectron spectroscopy

We investigated the valence electronic structure of diamondoid particles in the gas phase, utilizing valence photoelectron spectroscopy. The samples were singly or doubly covalently bonded dimers or trimers of the lower diamondoids. Both the bond type and the combination of bonding partners are shown to affect the overall electronic structure. For singly bonded particles, we observe a small impact of the bond on the electronic structure, whereas for doubly bonded particles, the connecting bond determines the electronic structure of the highest occupied orbitals. In the singly bonded particles a superposition of the bonding partner orbitals determines the overall electronic structure. The experimental findings are supported by density functional theory computations at the M06-2X/cc-pVDZ level of theory.

physics.atm-clus↗

arXiv2013

Derivation of a true (t->0+) quantum transition-state theory. II. Recovery of the exact quantum rate in the absence of recrossing

In Part I [J. Chem. Phys. 138, 084108 (2013)] we derived a quantum transition-state theory by taking the t->0+ (short-time) limit of a new form of quantum flux-side time-correlation function containing a ring-polymer dividing surface. This t->0+ limit appears to be unique in giving positive-definite Boltzmann statistics, and is identical to ring-polymer molecular dynamics (RPMD) TST. Here, we show that quantum TST (i.e. RPMD-TST) is exact if there is no recrossing (by the real-time quantum dynamics) of the ring-polymer dividing surface, nor of any surface orthogonal to it in the space describing fluctuations in the polymer-bead positions along the reaction coordinate. In practice, this means that RPMD-TST gives a good approximation to the exact quantum rate for direct reactions, provided the temperature is not too far below the cross-over to deep tunnelling. We derive these results by comparing the long-time limit of the ring-polymer flux-side time-correlation function with that of a hybrid flux-side time-correlation function (containing a ring-polymer flux operator and a Miller-Schwarz-Tromp side function), and by representing the resulting ring-polymer momentum integrals as hypercubes. Together with Part I, the results of this article validate a large number of RPMD calculations of reaction rates.

physics.chem-ph↗

arXiv2013

Homogeneous TIP4P/2005 ice nucleation at low supercooling

We present a partial free energy profile for the homogeneous nucleation of ice using an all-atom model of water at low supercooling, at which ice growth dynamics are reasonably accessible to simulation. We demonstrate that the free energy profile is well described by classical nucleation theory, and that the nucleation barrier is entropic in origin. We also estimate to first order the temperature dependence of the interfacial free energy.

physics.chem-ph↗

arXiv2013

Time-resolved broadband Raman spectroscopies; A unified six-wave-mixing representation

Excited-state vibrational dynamics in molecules can be studied by an electronically off-resonant Raman process induced by a probe pulse with variable delay with respect to an actinic pulse. We establish the connection between several variants of the technique that involve either spontaneous or stimulated Raman detection and different pulse configurations. By using loop diagrams in the frequency domain we show that all signals can be described as six wave mixing which depend on the same four point molecular correlation functions involving two transition dipoles and two polarizabilities and accompanied by a different gating. Simulations for the stochastic two-state-jump model illustrate the origin of the absorptive and dispersive features observed experimentally.

physics.chem-ph↗

arXiv2013

Alternative separation of exchange and correlation energies in multi-configuration range-separated density-functional theory

The alternative separation of exchange and correlation energies proposed by Toulouse et al. [Theor. Chem. Acc. 114, 305 (2005)] is explored in the context of multi-configuration range-separated density-functional theory. The new decomposition of the short-range exchange-correlation energy relies on the auxiliary long-range interacting wavefunction rather than the Kohn-Sham (KS) determinant. The advantage, relative to the traditional KS decomposition, is that the wavefunction part of the energy is now computed with the regular (fully-interacting) Hamiltonian. One potential drawback is that, because of double counting, the wavefunction used to compute the energy cannot be obtained by minimizing the energy expression with respect to the wavefunction parameters. The problem is overcome by using short-range optimized effective potentials (OEPs). The resulting combination of OEP techniques with wavefunction theory has been investigated in this work, at the Hartree-Fock (HF) and multi-configuration self-consistent-field (MCSCF) levels. In the HF case, an analytical expression for the energy gradient has been derived and implemented. Calculations have been performed within the short-range local density approximation on H2, N2, Li2 and H2O. Significant improvements in binding energies are obtained with the new decomposition of the short-range energy. The importance of optimizing the short-range OEP at the MCSCF level when static correlation becomes significant has also been demonstrated for H2, using a finite-difference gradient. The implementation of the analytical gradient for MCSCF wavefunctions is currently in progress.

physics.chem-ph↗

arXiv2014

On the Accuracy of van der Waals Inclusive Density-Functional Theory Exchange-Correlation Functionals for Ice at Ambient and High Pressures

Density-functional theory (DFT) has been widely used to study water and ice for at least 20 years. However, the reliability of different DFT exchange-correlation (xc) functionals for water remains a matter of considerable debate. This is particularly true in light of the recent development of DFT based methods that account for van der Waals (vdW) dispersion forces. Here, we report a detailed study with several xc functionals (semi-local, hybrid, and vdW inclusive approaches) on ice Ih and six proton ordered phases of ice. Consistent with our previous study [Phys. Rev. Lett. 107, 185701 (2011)] which showed that vdW forces become increasingly important at high pressures, we find here that all vdW inclusive methods considered improve the relative energies and transition pressures of the high-pressure ice phases compared to those obtained with semi-local or hybrid xc functionals. However, we also find that significant discrepancies between experiment and the vdW inclusive approaches remain in the cohesive properties of the various phases, causing certain phases to be absent from the phase diagram. Therefore, room for improvement in the description of water at ambient and high pressures remains and we suggest that because of the stern test the high pressure ice phases pose they should be used in future benchmark studies of simulation methods for water.

cond-mat.mtrl-sci↗

arXiv2013

Molecular Density Functional Theory of Water describing Hydrophobicity at Short and Long Length Scales

We present an extension of our recently introduced molecular density functional theory of water [G. Jeanmairet et al., J. Phys. Chem. Lett. 4, 619, 2013] to the solvation of hydrophobic solutes of various sizes, going from angstroms to nanometers. The theory is based on the quadratic expansion of the excess free energy in terms of two classical density fields, the particle density and the multipolar polarization density. Its implementation requires as input a molecular model of water and three measurable bulk properties, namely the structure factor and the k-dependent longitudinal and transverse dielectric susceptibilities. The fine three-dimensional water structure around small hydrophobic molecules is found to be well reproduced. In contrast the computed solvation free-energies appear overestimated and do not exhibit the correct qualitative behavior when the hydrophobic solute is grown in size. These shortcomings are corrected, in the spirit of the Lum-Chandler-Weeks theory, by complementing the functional with a truncated hard-sphere functional acting beyond quadratic order in density. It makes the resulting functional compatible with the Van-der-Waals theory of liquid-vapor coexistence at long range. Compared to available molecular simulations, the approach yields reasonable solvation structure and free energy of hard or soft spheres of increasing size, with a correct qualitative transition from a volume-driven to a surface-driven regime at the nanometer scale.

physics.chem-ph↗

arXiv2014

State-averaged Monte Carlo configuration interaction applied to electronically excited states

We introduce state-averaging into the method of Monte Carlo configuration interaction (SA-MCCI) to allow the stable and efficient calculation of excited states. We show that excited potential curves for H$_{3}$, including a crossing with the ground state, can be accurately reproduced using a small fraction of the FCI space. A recently introduced error measure for potential curves [J. P. Coe and M. J. Paterson, J. Chem. Phys., 137, 204108 (2012)] is shown to also be a fair approach when considering potential curves for multiple states. We demonstrate that potential curves for LiF using SA-MCCI agree well with the FCI results and the avoided crossing occurs correctly. The seam of conical intersections for CH$_{2}$ found by Yarkony [J. Chem. Phys., 104, 2932 (1996)] is used as a test for SA-MCCI and we compare potential curves from SA-MCCI with FCI results for this system for the first three triplet states. We then demonstrate the improvement from using SA-MCCI on the dipole of the $2$ $^{1}A_{1}$ state of carbon monoxide. We then look at vertical excitations for small organic molecules up to the size of butadiene where the SA-MCCI energies and oscillator strengths are compared with CASPT2 values [M. Schreiber, M. R. Silva-Junior, S. P. A. Sauer, and W. Thiel, J. Chem. Phys., 128, 134110 (2008)]. We finally see if the SA-MCCI results for these excitation energies can be improved by using MCCIPT2 with approximate natural orbitals when the PT2 space is not onerously large.

physics.chem-ph↗

arXiv2013

Sub-Ohmic spin-boson model with off-diagonal coupling: Ground state properties

We have carried out analytical and numerical studies of the spin-boson model in the sub-ohmic regime with the influence of both the diagonal and off-diagonal coupling accounted for via the Davydov D1 variational ansatz. While a second-order phase transition is known to be exhibited by this model in the presence of diagonal coupling only, we demonstrate the emergence of a discontinuous first order phase transition upon incorporation of the off-diagonal coupling. A plot of the ground state energy versus magnetization highlights the discontinuous nature of the transition between the isotropic (zero magnetization) state and nematic (finite magnetization) phases. We have also calculated the entanglement entropy and a discontinuity found at a critical coupling strength further supports the discontinuous crossover in the spin-boson model in the presence of off-diagonal coupling. It is further revealed via a canonical transformation approach that for the special case of identical exponents for the spectral densities of the diagonal and the off-diagonal coupling, there exists a continuous crossover from a single localized phase to doubly degenerate localized phase with differing magnetizations.

cond-mat.str-el↗

arXiv2013

Dipolar Poisson-Boltzmann Approach to Ionic Solutions: A Mean Field and Loop Expansion Analysis

We study the variation of the dielectric response of ionic aqueous solutions as function of their ionic strength. The effect of salt on the dielectric constant appears through the coupling between ions and dipolar water molecules. On a mean-field level, we account for any internal charge distribution of particles. The dipolar degrees of freedom are added to the ionic ones and result in a generalization of the Poisson-Boltzmann (PB) equation called the Dipolar PB (DPB). By looking at the DPB equation around a fixed point-like ion, a closed-form formula for the dielectric constant is obtained. We express the dielectric constant using the "hydration length" that characterizes the hydration shell of dipoles around ions, and thus the strength of the dielectric decrement. The DPB equation is then examined for three additional cases: mixture of solvents, polarizable medium and ions of finite size. Employing field-theoretical methods we expand the Gibbs free-energy to first order in a loop expansion and calculate self-consistently the dielectric constant. For pure water, the dipolar fluctuations represent an important correction to the mean-field value and good agreement with the water dielectric constant is obtained. For ionic solutions we predict analytically the dielectric decrement that depends on the ionic strength in a non-linear way. Our prediction fits rather well a large range of concentrations for different salts using only one fit parameter related to the size of ions and dipoles. A linear dependence of the dielectric constant on the salt concentration is observed at low salinity, and a noticeable deviation from linearity can be seen for ionic strength above 1\,M, in agreement with experiments.

cond-mat.soft↗

arXiv2013

Tension moderation and fluctuation spectrum in simulated lipid membranes under an applied electric potential

We investigate the effect of an applied electric potential on the mechanics of a coarse grained POPC bilayer under tension. The size and duration of our simulations allow for a detailed and accurate study of the fluctuations. Effects on the fluctuation spectrum, tension, bending rigidity, and bilayer thickness are investigated in detail. In particular, the least square fitting technique is used to calculate the fluctuation spectra. The simulations confirm a recently proposed theory that the effect of an applied electric potential on the membrane will be moderated by the elastic properties of the membrane. In agreement with the theory, we find that the larger the initial tension the larger the effect of the electric potential. Application of the electric potential increases the amplitude of the long wavelength part of the spectrum and the bending rigidity is deduced from the short wavelength fluctuations. The effect of the applied electric potential on the bending rigidity is non-existent within error bars. However, when the membrane is stretched there is a point where the bending rigidity is lowered due to a decrease of the thickness of the membrane. All these effects should prove important for mechanosensitive channels and biomembrane mechanics in general.

physics.chem-ph↗

arXiv2013

Extended Lagrangian Born-Oppenheimer molecular dynamics in the limit of vanishing self-consistent field optimization

We present an efficient general approach to first principles molecular dynamics simulations based on extended Lagrangian Born-Oppenheimer molecular dynamics in the limit of vanishing self-consistent field optimization. The reduction of the optimization requirement reduces the computational cost to a minimum, but without causing any significant loss of accuracy or longterm energy drift. The optimization-free first principles molecular dynamics requires only one single diagonalization per time step and yields trajectories at the same level of accuracy as "exact", fully converged, Born-Oppenheimer molecular dynamics simulations. The optimization-free limit of extended Lagrangian Born-Oppenheimer molecular dynamics therefore represents an ideal starting point for a robust and efficient formulation of a new generation first principles quantum mechanical molecular dynamics simulation schemes.

physics.chem-ph↗

arXiv2013

Resummed thermodynamic perturbation theory for bond cooperativity in associating fluids

We develop a resummed thermodynamic perturbation theory for bond cooperativity in associating fluids by extension of Wertheim's multi - density formalism. We specifically consider the case of an associating hard sphere with two association sites and both pairwise and triplet contributions to the energy. To test the theory we perform new monte carlo simulations. Theory and simulation are found to be in excellent agreement.

cond-mat.soft↗

arXiv2013

Theoretical study of ThO for the electron electric dipole moment search

An experiment to search for the electron electric dipole moment (\eEDM) on the metastable $H^3Δ_1$ state of ThO molecule was proposed and now in the final stage of preparation by the ACME collaboration [http://www.electronedm.org]. To interpret the experiment in terms of \eEDM\ and dimensionless constant $k_{T,P}$ characterizing the strength of the scalar T,P-odd electron-nucleus neutral current interaction, an accurate theoretical study of effective electric field on electron, Eeff, and $W_{T,P}$ constants is required. We report calculation of \Eeff\ (84 GV/cm) and a parameter of T,P-odd scalar neutral currents interaction, $W_{T,P}$ (116 kHz), together with the hyperfine structure constant, molecule frame dipole moment and $H^3Δ_1\to X^1Σ^+$ transition energy, which can serve as a measure of reliability of the obtained \Eeff\ and $W_{T,P}$ values. Besides, our results include a parity assignment and evaluation of the electric-field dependence for the magnetic $g$ factors for the $Ω$-doublets of $H^3Δ_1$.

physics.chem-ph↗

arXiv2013

Mixed-field orientation of molecules without rotational symmetry

The mixed-field orientation of an asymmetric-rotor molecule with its permanent dipole moment non-parallel to the principal axes of polarizability is investigated experimentally and theoretically. We find that for the typical case of a strong, nonresonant laser field and a weak static electric field complete 3D orientation is induced if the laser field is elliptically polarized and if its major and minor polarization axes are not parallel to the static field. For a linearly polarized laser field solely the dipole moment component along the most polarizable axis of the molecule is relevant resulting in 1D orientation even when the laser polarization and the static field are non parallel. Simulations show that the dipole moment component perpendicular to the most-polarizable axis becomes relevant in a strong dc electric field combined with the laser field. This offers an alternative approach to 3D orientation by combining a linearly-polarized laser field and a strong dc electric field arranged at an angle equal to the angle between the most polarizable axis of the molecule and its permanent dipole moment.

physics.chem-ph↗