Velocity Autocorrelation Function Research Articles

Dynamical coarse-grained models of molecular liquids and their ideal and non-ideal mixtures.

Coarse-grained (CG) simulation models of condensed-phase systems can be derived with well-established methods that perform coarse-graining in space and provide an effective Hamiltonian with which some of the structural and thermodynamic properties of the underlying fine-grained (FG) reference system can be represented. Coarse-graining in time potentially provides CG models that furthermore represent dynamic properties. However, systematic efforts in this direction have so far been limited, especially for moderately coarse-grained, chemistry-specific systems with complicated conservative interactions. With the aim of representing structural, thermodynamic, and dynamic properties in CG simulations of multi-component molecular systems, we investigated a recently introduced method in which the force on a CG particle originates from conservative interactions with surrounding particles and non-Markovian dissipative interactions, the latter introduced by means of a colored-noise thermostat. We examined two different methods to derive isotropic memory kernels required for integrating the corresponding generalized Langevin equation (GLE) of motion, based on the orthogonal dynamics of the FG forces and on an iterative optimization scheme. As a proof of concept, we coarse-grain single-component molecular liquids (cyclohexane, tetrachloromethane) and ideal and non-ideal binary mixtures of cyclohexane/tetrachloromethane and ethanol/tetrachloromethane, respectively. We find that for all systems, the FG single particle velocity auto-correlation functions and, consequently, both the short time and long time diffusion coefficients can be quantitatively reproduced with the CG-GLE models. We furthermore demonstrate that the present GLE-approach leads to an improved description of the rate with which the spatial correlations decay, which is artificially accelerated in the absence of dissipation.

Differences in the Effect of Water on Deep Eutectic Solvents Based on Choline Chloride/Lauric Acid and Choline Chloride/Myristic Acid: Molecular Dynamics Simulations at Three Different Temperatures

AbstractApplication of deep eutectic solvents based on fatty acids in different fields of biological and therapeutic sciences, such as novel hydrophobic Volatile organic compounds (VOC) absorbents, etc. However, industries need knowledge and precise investigation of the structural and dynamic properties of these solvents. In this work, the effect of water on the dynamical and structural properties of the binary mixtures of choline chloride+two types of Fatty acids; Lauric (LUA), and Myristic (MRA) acids have been investigated at T=343 K, 443 K, 543 K. An additional NPT production run of 30 ns was considered for the binary mixtures. In order to understand the effective interactions in the formation of the eutectic mixture based on fatty acid and choline chloride, the combined distribution functions (CDFs) involving the radial distribution functions (RDFs) and the angular distribution functions (ADFs), the hydrogen‐bonding network, and spatial distribution functions (SDFs), interaction energies between species were calculated for the binary mixtures. Also, the dynamical properties of DESs have been evaluated by calculating the mean‐square displacement (MSD), the velocity autocorrelation function (VACF) of the centers of mass of the molecules, and the self‐diffusion coefficient.

Dynamics of an impurity ion transport in oil‐paper insulation under various electric fields

AbstractThe ionic transport process is an important counterpart to charge transport in oil‐paper insulation, and it significantly impacts oil flow electrification at the oil‐paper interface. Despite this, the dynamics of this phenomenon and the underlying mechanisms remain unclear, particularly at the molecular level. To understand this fundamental aspect, we conduct Molecular Dynamics study on the transport behaviour of an impurity ion in different oil‐paper insulation models under various external electric fields. Different influence factors, such as external electric fields, temperatures, and local structural characteristics, are investigated in relation to the corresponding ionic mobility in different polymer models. According to the simulations, ionic mobility and its response to electric fields are higher in weaker electrostatic models. As a result, mineral oil exhibits the highest ionic mobility and the most substantial enhancement of ionic mobility by external electric fields, followed by vegetable oil, oil‐paper blends, and insulating paper. This significant deviation in ionic mobility between oil and paper leads to the formation of an electric double layer near the oil‐paper interface. The underlying physical mechanisms of different ionic mobility and its response to the electric field in different polymer models could be explained by the different polymer structural influences in terms of interaction energy and coordination numbers in a static manner, as well as by the interactions between the impurity ion and its surrounding atoms in terms of lifetime correlation functions and velocity autocorrelation functions in a dynamic manner. In addition, the influence of temperature on ionic mobility in mineral and vegetable oil is examined, and their activation energies are calculated. Advancing in the fundamental understanding of the dynamics of the ion transport process in oil‐paper insulation is vital to improving their insulating properties for oil‐impregnated power transformers.

Molecular hydrodynamic theory of the velocity autocorrelation function.

The velocity autocorrelation function (VACF) encapsulates extensive information about a fluid's molecular-structural and hydrodynamic properties. We address the following fundamental question: How well can a purely hydrodynamic description recover the molecular features of a fluid as exhibited by the VACF? To this end, we formulate a bona fide hydrodynamic theory of the tagged-particle VACF for simple fluids. Our approach is distinguished from previous efforts in two key ways: collective hydrodynamic modes and tagged-particle self-motion are modeled by linear hydrodynamic equations; the fluid's spatial velocity power spectrum is identified as a necessary initial condition for the momentum current correlation. This formulation leads to a natural physical interpretation of the VACF as a superposition of products of quasinormal hydrodynamic modes weighted commensurately with the spatial velocity power spectrum, the latter of which appears to physically bridge continuum hydrodynamical behavior and discrete-particle kinetics. The methodology yields VACF calculations quantitatively on par with existing approaches for liquid noble gases and alkali metals. Furthermore, we obtain a new, hydrodynamic form of the self-intermediate scattering function whose description has been extended to low densities where the Schmidt number is of order unity; various calculations are performed for gaseous and supercritical argon to support the general validity of the theory. Excellent quantitative agreement is obtained with recent MD calculations for a dense supercritical Lennard-Jones fluid.

Dynamical behavior and transport coefficients of the pseudo hard-sphere fluid

In this work, we employ a recent approach to characterize the hard-sphere (HS) fluid by means of a continuous interaction potential, commonly referred to as pseudo hard-sphere potential, in order to determine HS transport coefficients as a function of the volume fraction for the three-dimensional mono disperse fluid. Using equilibrium molecular dynamics simulations, we determine time-dependent velocity, shear stress, and energy flux autocorrelation functions in order to use them within the Green–Kubo framework to compute the self-diffusion, shear viscosity, and thermal conductivity coefficients, respectively. Results are discussed as a function of the volume fraction and were compared to theoretical and simulations results previously reported by other authors. The main purpose of this work is twofold: first, testing the continuous approach of the HS fluid for the computation of dynamic properties and second, performing a systematic determination of aforementioned transport coefficients to analyze them as a function of fluid volume fraction. Furthermore, our results are used to provide a practical correction to the Chapman–Enskog equations for the HS self-diffusion, shear viscosity, and thermal conductivity predictions in a wide range of volume fractions.

Nonequilibrium diffusion of active particles bound to a semiflexible polymer network: Simulations and fractional Langevin equation.

In a viscoelastic environment, the diffusion of a particle becomes non-Markovian due to the memory effect. An open question concerns quantitatively explaining how self-propulsion particles with directional memory diffuse in such a medium. Based on simulations and analytic theory, we address this issue with active viscoelastic systems where an active particle is connected with multiple semiflexible filaments. Our Langevin dynamics simulations show that the active cross-linker displays superdiffusive and subdiffusive athermal motion with a time-dependent anomalous exponent α. In such viscoelastic feedback, the active particle always exhibits superdiffusion with α = 3/2 at times shorter than the self-propulsion time (τA). At times greater than τA, the subdiffusive motion emerges with α bounded between 1/2 and 3/4. Remarkably, active subdiffusion is reinforced as the active propulsion (Pe) is more vigorous. In the high Pe limit, athermal fluctuation in the stiff filament eventually leads to α = 1/2, which can be misinterpreted with the thermal Rouse motion in a flexible chain. We demonstrate that the motion of active particles cross-linking a network of semiflexible filaments can be governed by a fractional Langevin equation combined with fractional Gaussian noise and an Ornstein-Uhlenbeck noise. We analytically derive the velocity autocorrelation function and mean-squared displacement of the model, explaining their scaling relations as well as the prefactors. We find that there exist the threshold Pe (Pe∗) and crossover times (τ∗ and τ†) above which active viscoelastic dynamics emerge on timescales of τ∗≲ t ≲ τ†. Our study may provide theoretical insight into various nonequilibrium active dynamics in intracellular viscoelastic environments.

Ergodic Measure and Potential Control of Anomalous Diffusion.

In statistical mechanics, the ergodic hypothesis (i.e., the long-time average is the same as the ensemble average) accompanying anomalous diffusion has become a continuous topic of research, being closely related to irreversibility and increasing entropy. While measurement time is finite for a given process, the time average of an observable quantity might be a random variable, whose distribution width narrows with time, and one wonders how long it takes for the convergence rate to become a constant. This is also the premise of ergodic establishment, because the ensemble average is always equal to the constant. We focus on the time-dependent fluctuation width for the time average of both the velocity and kinetic energy of a force-free particle described by the generalized Langevin equation, where the stationary velocity autocorrelation function is considered. Subsequently, the shortest time scale can be estimated for a system transferring from a stationary state to an effective ergodic state. Moreover, a logarithmic spatial potential is used to modulate the processes associated with free ballistic diffusion and the control of diffusion, as well as the minimal realization of the whole power-law regime. The results presented suggest that non-ergodicity mimics the sparseness of the medium and reveals the unique role of logarithmic potential in modulating diffusion behavior.

MolTwister – a molecular systems construction, manipulation and statistical mechanical calculation tool

To perform molecular dynamics (MD) simulations, Monte Carlo (MC) simulations, quantum mechanical (QM) electronic structure calculations, or similar atomistic calculations, it is necessary to first construct and define the molecular system of interest. This involves creating an initial configuration of atoms, where MD and MC simulations require forcefield assignments, for example in the form of non-bonded, bonded, angular and dihedral potentials. Once simulations or calculations have been performed, large sets of data are available (often several gigabytes). These contain atomic trajectories and other relevant static or dynamic information, from which static and dynamic properties (such as density profiles, vibrational density of states and velocity autocorrelation functions) can be obtained through statistical mechanical calculations. MolTwister is an open source software platform that addresses the construction of molecular systems, basic 3D visualization of these, the generation of input files for selected MD packages, as well as calculation of properties from atomistic simulation data. It also contains a GPU accelerated MD simulator suited for smaller tasks such as molecular thermalization. The software package is written in C++14 and can be used as a basis for further development, where efforts have been made to make access to underlying functionality easy. Moreover, it supports Python, where scripts have access to the majority of program functionality. Program summaryProgram Title: MolTwisterCPC Library link to program files:https://doi.org/10.17632/ph6pwst9mn.1Developer's repository link:http://moltwister.comLicensing provisions: GPLv3 or laterProgramming language: C++14Nature of problem: Lack of SW tools for easy construction of complex molecular systems, as well as tools enabling analysis of long molecular trajectories.Solution method: Developed command line tool with associated 3D view, where molecular construction commands can be executed in complex manners through a Python interface. The program also has commands for analysis of molecular data that process one molecular time-frame at a time, thus enabling analysis of long molecular trajectories. Moreover, the program structure is designed for easy implementation of new commands by other researchers.Additional comments including restrictions and unusual features: Supported file formats: xyz, pdb, mtt (MolTwister trajectory), dcd, xtc, qepos, python, script (MolTwister scripts)Supported MD engines: HOOMD-blue, LAMMPS, MolTwister internal (moldyn)

Frequency-dependent hydrodynamic finite size correction in molecular simulations reveals the long-time hydrodynamic tail.

Finite-size effects are challenging in molecular dynamics simulations because they have significant effects on computed static and dynamic properties, in particular diffusion constants, friction coefficients, and time- or frequency-dependent response functions. We investigate the influence of periodic boundary conditions on the velocity autocorrelation function and the frequency-dependent friction of a particle in a fluid, and show that the long-time behavior (starting at the picosecond timescale) is significantly affected. We develop an analytical correction allowing us to subtract the periodic boundary condition effects. By this, we unmask the power-law long-time tails of the memory kernel and the velocity autocorrelation function in liquid water and a Lennard-Jones fluid from simulations with rather small box sizes.

Lattice thermal conductivity of cubic GeTe with vacancy defects

Germanium telluride (GeTe) and its variants are promising compounds as high figure of merit thermoelectric materials due to their low lattice thermal conductivity. The strong anharmonicity and the intrinsic Ge vacancies are shown to be the origin of the low thermal conductivity. While the anharmonic effect on the lattice thermal conductivity has been systematically studied using the perturbation theory, the vacancy disorder has been treated perturbatively mostly as an extreme case of phonon-isotope scattering. This simplification ignores realistic features such as the nonbonding character and the detailed local environments near the vacancies. In this study, we calculate the lattice thermal conductivity of the cubic GeTe by considering the anharmonicity and the vacancy disorder on the same footing using the machine-learning potential molecular dynamics. We obtain the spectral function via the nonperturbative approaches, the velocity autocorrelation function, and the phonon unfolding scheme to investigate the effect of the vacancies on the lattice thermal conductivity. We find that the reduction in the lattice thermal conductivity by the vacancies originates from the momentum-dependent scattering of the acoustic phonon modes and the momentum-independent scattering of the optical phonon modes as determined by the strength of the anharmonicity.

Simulation study of the collective excitations in liquid sodium under high pressure

The dynamic structure of liquid sodium is investigated using classical molecular dynamics simulations over a wide range of densities (from 739 to 4177 kg m−3). The interactions are described using screened pseudopotential formalism with Fiolhais model of electron-ion interaction. The effective pair potentials obtained are validated by comparing the predicted static structure, coordination number, self-diffusion coefficients and spectral density of the velocity autocorrelation function with results from ab initio simulations at the same state points. Both longitudinal and transverse collective excitations are computed from the corresponding structure functions and their evolution with density is investigated. The frequency of the longitudinal excitations increases with density, as well as the sound speed, which is extracted from their dispersion curves. The frequency of the transverse excitations also increases with density, but they cannot propagate over macroscopic distances and the propagation gap clearly appears. The values of the viscosity, which are extracted from these transverse functions are in good agreement with available results computed from stress autocorrelation functions.

On the binary diffusion coefficients of n-alkanes in He/N2

The binary diffusion coefficients of fuel molecules in bath gasses are key parameters for accurate predictions of flame properties such as extinction strain rates. In combustion simulations, they are often calculated using the Hirschfelder-Bird-Spotz (HBS) equation, which requires the availability of effective Lennard-Jones parameters, i.e. collision diameters and well depths, which can be obtained from the intermolecular potentials of two interacting species by applying an orientation-averaging rule. Besides the HBS equation, the Green-Kubo formula can be used to obtain binary diffusion coefficients, using velocity autocorrelation and cross-correlation functions from molecular dynamics simulations. In this work, we propose a new orientation-averaging rule, called VolW-σ-ε, based on the characteristic of intermolecular potentials, and evaluate different approaches to computing the diffusion coefficients of n-alkanes in He/N2 mixtures. Several orientation-averaging rules are evaluated and compared with experimental data of n-alkanes in He and N2 and the results of molecular dynamics simulations. Finally, using the binary diffusion coefficients of n-dodecane in N2 evaluated by the VolW-σ-ε method, we reproduce previously reported experimental extinction strain rates reported for counterflow n-dodecane/N2 versus O2 jets.

Revealing the supercritical dynamics of dusty plasmas and their liquidlike to gaslike dynamical crossover

Dusty plasmas represent a powerful playground to study the collective dynamics of strongly coupled systems with important interdisciplinary connections to condensed matter physics. Due to the pure Yukawa repulsive interaction between dust particles, dusty plasmas do not display a traditional liquid-vapor phase transition, perfectly matching the definition of a supercritical fluid. Using molecular dynamics simulations, we verify the supercritical nature of dusty plasmas and reveal the existence of a dynamical liquid-like to gas-like crossover which perfectly matches the salient features of the Frenkel line in classical supercritical fluids. We present several diagnostics to locate this dynamical crossover spanning from local atomic connectivity, shear relaxation dynamics, velocity autocorrelation function, heat capacity, and various transport properties. All these different criteria well agree with each other and are able to successfully locate the Frenkel line in both 2D and 3D dusty plasmas. In addition, we propose the unity ratio of the instantaneous transverse sound speed $C_T$ to the average particle speed $\bar{v}_{p}$, i.e., $C_T / \bar{v}_{p} = 1$, as a new diagnostic to identify this dynamical crossover. Finally, we observe an emergent degree of universality in the collective dynamics and transport properties of dusty plasmas as a function of the screening parameter and dimensionality of the system. Intriguingly, the temperature of the dynamical transition is independent of the dimensionality, and it is found to be always $20$ times of the corresponding melting point. Our results open a new path for the study of single particle and collective dynamics in plasmas and their interrelation with supercritical fluids in general.

Bottom-Up Informed and Iteratively Optimized Coarse-Grained Non-Markovian Water Models with Accurate Dynamics.

Molecular dynamics (MD) simulations based on coarse-grained (CG) particle models of molecular liquids generally predict accelerated dynamics and misrepresent the time scales for molecular vibrations and diffusive motions. The parametrization of Generalized Langevin Equation (GLE) thermostats based on the microscopic dynamics of the fine-grained model provides a promising route to address this issue, in conjunction with the conservative interactions of the CG model obtained with standard coarse graining methods, such as iterative Boltzmann inversion, force matching, or relative entropy minimization. We report the application of a recently introduced bottom-up dynamic coarse graining method, based on the Mori-Zwanzig formalism, which provides accurate estimates of isotropic GLE memory kernels for several CG models of liquid water. We demonstrate that, with an additional iterative optimization of the memory kernels (IOMK) for the CG water models based on a practical iterative optimization technique, the velocity autocorrelation function of liquid water can be represented very accurately within a few iterations. By considering the distinct Van Hove function, we demonstrate that, with the presented methods, an accurate representation of structural relaxation can be achieved. We consider several distinct CG potentials to study how the choice of the CG potential affects the performance of bottom-up informed and iteratively optimized models.

Structure and Dynamics in Liquid Iron at High Pressure and Temperature. A First Principles Study

AbstractWe have studied the evolution of structural and dynamic properties of liquid Fe as a function of pressure for 11 thermodynamic states close to the melting line. The pressure range considered goes from ambient pressure to 323 GPa, and the study has been carried out by using the ab‐initio molecular dynamics technique. The agreement between the calculated static structure and the available experimental data is very good, including details like an asymmetric second peak, which remains over most of the whole pressure range and suggests a significant local icosahedral short‐range order in the liquid. The dynamical structure is studied through the characteristics of the propagating density fluctuations and the associated longitudinal and transverse particle currents. The transverse dispersion relations expose two branches of modes for all pressures, whose range of appearance is analyzed and put in connection with the double‐peak structure of the Fourier spectra of velocity autocorrelation functions. We have also investigated the existence of fingerprints of transverse acoustic excitation modes in the dynamic structure factor for the high pressure states similar to those observed in the inelastic X‐ray scattering intensity data of liquid Fe at ambient pressure. The calculated electronic density of states shows that with increasing pressure there is a widening of the conduction band along with a decreasing significance of spin polarization. Finally, we also report results for transport coefficients like self‐diffusion, shear viscosity and adiabatic sound velocity, which are compared with the available experimental data.

Dynamic properties of decane/water microemulsions decorated with hydrophobically modified PEO Polymer (PEO-C12): A molecular dynamics simulations study

This work aims to probe the dynamics of Microemulsions/PEO complexes by using Molecular dynamics simulations (MD). The studied system is a highly diluted O/W charged MEs (Φ = 2.8%), covered by significant amounts of PEO polymer chains, with a short sticky block PEO-C12 (Np = 0, 4, 8, 12, 16, 24 and 32). The employed effective pair potential is a combination of a hard sphere, the van der Waals and a Yukawa type potential. I order to shed light on the dynamic properties of this system, we analyzed the mean-squared displacement (MSD), the diffusion coefficients (Dc) and the velocity autocorrelation function (VACF) as a number Np of added PEO-C12; Increasing the polymer concentration Np slows down the diffusion of the system.

On the existence of a second branch of transverse collective excitations in liquid metals

It was found recently that the liquid dynamics of several metals (Li, Zn, Ni, Fe, Tl, Pb) under pressure is characterized by transverse spectral functions containing an additional high-frequency peak. To rationalize the pressure dependence of the contributions from different propagating processes to transverse spectral functions in liquid metals, ab initio molecular dynamics simulations were performed for two typical liquid metals (Na and Al) in a wide range of pressures. The influence of density/pressure is investigated for Na by considering four pressures ranging from 15 to 147 GPa, while the temperature influence is considered for Al between 600 K in the deep supercooled liquid up to 1700 K well above the melting point at ambient pressure. Both temperature and density dependence of the spectra of collective excitations are analyzed with a focus on the appearance of a second high-frequency mode in the transverse spectra. A correspondence between spectra of transverse collective excitations and the peak positions of the Fourier-spectra of velocity autocorrelation functions (vibrational density of states) is found.

Tracing the Effect of Replacing [Gly]- with [Ala]- and Hydroxylation of [emim]+ on the Fine-Tuning of the Transport Properties of the Corresponding Amino Acid-Based Ionic Liquids Using MD Simulation.

Natural amino acid-based ionic liquids (AAILs) composed of deprotonated amino acids, [AA]-, as anions and hydroxylated imidazolium cations provide an eco-friendly nontoxic IL family with the growing number of chemical and biochemical revolutionary applications. In this paper, the transport properties of four AAILs composed of 1-(2-hydroxyethyl)-3-methylimidazolium ([HOemim]+) and 1-ethyl-3-methylimidazolium ([emim]+) cations with alaninate and glycinate anions were studied by molecular dynamics (MD) simulations. A nonpolarizable all-atom force field with the scaled charge (±0.8e) on each of the ions was applied and compared with the unit charge model in some cases. The tunable effects of the presence of the hydroxyl group in the side chain of the imidazolium cation, the type of amino acid anion, and the varied temperature on the dynamical behavior of AAILs were investigated in detail. The experimentally compatible trends of the simulated ionic self-diffusion coefficients, ionic conductivity, and ionicity were found to be inverse to the viscosity and ionic association of these ILs as [emim][Gly] > [emim][Ala] > [HOemim][Gly] > [HOemim][Ala]. The main reason behind these trends is the higher ability of the hydroxylated cation for the hydrogen-bond formation with [AA]-. The mean square displacement (MSD), self-diffusion, and transference number of imidazolium cations are larger than those of [AA]- anions, except in the case of [HOemim][Gly]. It was found that the activation energy for diffusion of [AA]- is lower than that of [HOemim]+ but higher than that of [emim]+ in [HOemim][AA] and [emim][AA] ILs, respectively. The computed velocity autocorrelation function (VACF) showed that [Gly]-, as the lightest ion, has the shortest mean collision time and velocity randomization time among the ions, especially in the [HOemim][Gly] IL. Replacing [emim]+ with [HOemim]+, similar to the effect of decreasing temperature, causes significant decreasing of the ionic self-diffusion and increasing of the well depth of the first minimum of the ionic VACFs. Current findings show that introducing suitable functional groups in the side chain of imidazolium cations can be a viable approach for efficient engineering design and fine-tuning of the transport properties of these AAILs.

Collective dynamics in liquid Si under high pressure above the melting line minimum

We report an ab initio simulation study of changes in structural and dynamic properties of liquid Si at 7 pressures ranging from 10.2 to 24.3 GPa along the isothermal line 1150 K, which is above the minimum of the melting line. The increase of pressure from 10.2 to 16 GPa causes strong reduction in the tetrahedral ordering of the closest neighbors. The diffusion coefficient shows a linear decay vs drop in atomic volume, that agrees with theoretical prediction for simple liquid metals, thus not showing any feature at the pressures corresponding to the different crystal phase boundaries. The Fourier-spectrum of the velocity autocorrelation function shows two-peak structure at pressures 20 of GPa and higher. These characteristic frequencies correspond well to the peak frequencies of the transverse current spectral function in the second pseudo-Brillouin zone. Two almost flat branches of short-wavelength transverse modes were observed at all the studied pressures. We discuss the pressure evolution of characteristic frequencies in the longitudinal and transverse branches of collective modes.

Exploring the Dynamical Nature of Intermolecular Hydrogen Bonds in Benzamide, Quinoline and Benzoic Acid Derivatives.

The hydrogen bonds properties of 2,6-difluorobenzamide, 5-hydroxyquinoline and 4-hydroxybenzoic acid were investigated by Car-Parrinello and path integral molecular dynamics (CPMD and PIMD), respectively. The computations were carried out in vacuo and in the crystalline phase. The studied complexes possess diverse networks of intermolecular hydrogen bonds (N-H…O, O-H…N and O-H…O). The time evolution of hydrogen bridges gave a deeper insight into bonds dynamics, showing that bridged protons are mostly localized on the donor side; however, the proton transfer phenomenon was registered as well. The vibrational features associated with O-H and N-H stretching were analyzed on the basis of the Fourier transform of the atomic velocity autocorrelation function. The spectroscopic effects of hydrogen bond formation were studied. The PIMD revealed quantum effects influencing the hydrogen bridges providing more accurate free energy sampling. It was found that the N…O or O…O interatomic distances decreased (reducing the length of the hydrogen bridge), while the O-H or N-H covalent bond was elongated, which led to the increase in the proton sharing. Furthermore, Quantum Theory of Atoms in Molecules (QTAIM) was used to give insight into electronic structure parameters. Finally, Symmetry-Adapted Perturbation Theory (SAPT) was employed to estimate the energy contributions to the interaction energy of the selected dimers.