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We propose a simple estimator that allows to calculate the absolute value of a system's partition function from a finite sampling of its canonical ensemble. The estimator utilizes a volume correction term to compensate the effect that the finite sampling cannot cover the whole configuration space. As a proof of concept, the estimator is applied to calculate the partition function for several model systems, and the results are compared with the numerically exact solutions. Excellent agreement is found, demonstrating that a solution for an efficient calculation of partition functions is possible.

Inspired by the recent development on calculating the free energy change via a relaxation process [Nat. Phys. 14, 842 (2018)], we investigate the role of heat released in an irreversible relaxation following a large perturbation. Utilizing a derivation without microscopic reversibility, we arrive at a new free energy estimator that employs a volume term to account for missing important rare events. Applications to harmonic oscillators and particle insertion in Lennard-Jones fluid agree well with the (numerical) exact solutions. Our study hence suggests an alternative interpretation to the insufficient sampling problem in free energy calculations.

Quantum molecular dynamics simulations with MCTDH or ML-MCTDH perform best if the potential energy surface (PES) has a sum-of-products (SOP) or multi-layer operator (MLOp) structure. Here we investigate four different POTFIT-based methods for representing a general PES as such a structure, among them the novel random-sampling multi-layer Potfit (RS-MLPF). We study how the format and accuracy of the PES representation influences the runtime of a benchmark (ML-)MCTDH calculation, namely the computation of the ground state of the ${\text{H}_3\text{O}_2}^-$ ion. Our results show that compared to the SOP format, the MLOp format leads to a much more favorable scaling of the (ML-)MCTDH runtime with the PES accuracy. At reasonably high PES accuracy, ML-MCTDH calculations thus become up to 20 times faster, and taken to the extreme, the RS-MLPF method yields extremely accurate PES representations (global root-mean-square error of $\sim 0.1\,\text{cm}^{-1}$) which still lead to only moderate computational demands for ML-MCTDH., Comment: (C) 2017. This manuscript version is made available under the CC-BY-NC-ND 4.0 license. http://creativecommons.org/licenses/by-nc-nd/4.0/

Free energy perturbation (FEP) is frequently used to evaluate the free energy change of a biological process, e.g. the drug binding free energy or the ligand solvation free energy. Due to the sampling inefficiency, FEP is often employed together with computationally expensive enhanced sampling methods. Here we show that this sampling inefficiency, which stems from not accounting for the environmental reorganization, is an inherent property of the single-ensemble ansatz of FEP, and hence simply prolonging the MD simulation can hardly alleviate the problem. Instead, we propose a new, multi-ensemble ansatz -- the multi-layer free energy perturbation (MLFEP), which allows environmental reorganization processes (relaxation) to occur automatically during the MD sampling. Our study paves the way toward a fast but accurate free energy calculation that can be employed in computer-aided drug design.

The complex interplay between turbulence, magnetic fields, and self-gravity leads to the formation of molecular clouds out of the diffuse interstellar medium (ISM). One avenue of studying this interplay is by analyzing statistical features derived from observations, where the interpretation of these features is greatly facilitated by comparisons with numerical simulations. Here we focus on the statistical anisotropy present in synthetic maps of velocity centroid data, which we derive from three-dimensional magnetohydrodynamic simulations of a turbulent, magnetized, self-gravitating patch of ISM. We study how the orientation and magnitude of the velocity anisotropy correlate with the magnetic field and with the structures generated by gravitational collapse. Motivated by recent observational constraints, our simulations focus on the supersonic (sonic Mach number $\mathcal{M} \approx 2 - 17$) but sub- to trans-alfvenic (alfvenic Mach number $\mathcal{M}_A \approx 0.2 - 1.2$) turbulence regime, and we consider clouds which are barely to mildly magnetically supercritical (mass-to-flux ratio equal to once or twice the critical value). Additionally we explore the impact of the turbulence driving mechanism (solenoidal or compressive) on the velocity anisotropy. While we confirm previous findings that the velocity anisotropy generally aligns well with the plane-of-sky magnetic field, our inclusion of the effects of self-gravity reveals that in regions of higher column density, the velocity anisotropy may be destroyed or even reoriented to align with the gravitationally formed structures. We provide evidence that this effect is not necessarily due to the increase of $\mathcal{M}_A$ inside the high-density regions., Comment: 18 pages, 15 figures. Accepted for publication in ApJ

Most molecular clouds are filamentary or elongated. Among those forming low-mass stars, their long axes tend to be either parallel or perpendicular to the large-scale (10-100 pc) magnetic field (B-field) in the surrounding inter cloud medium. This arises because, along the dynamically dominant B-fields, the competition between self-gravity and turbulent pressure will shape the cloud to be elongated either perpendicular or parallel to the fields. Recent study also suggested that, on the scales of 0.1-0.01 pc, fields are dynamically important within cloud cores forming massive stars. But whether the core field morphologies are inherited from the inter cloud medium or governed by cloud turbulence is under vigorous debate, so is the role played by B-fields in cloud fragmentation at 10 - 0.1 pc scales. Here we report B-field maps covering 100-0.01 pc scales inferred from polarimetric observations of a massive-star forming region, NGC 6334. First, the main filament also lies perpendicular to the ambient field. NGC 6334 hosts young star-forming sites where fields are not severely affected by stellar feedback, and their directions do not change significantly over the entire scale range. This means that the fields are dynamically important. At various scales, we find that the hourglass-shaped field lines are pinched where the gas column density peaks and the field strength is proportional to the 0.4-power of the density. We conclude that B-fields play a crucial role in the fragmentation of NGC 6334., Comment: 16 pages, 6 figures

We investigate the exact wavefunction as a single product of electronic and nuclear wavefunction for a model conical intersection system. Exact factorized spiky potentials and nodeless nuclear wavefunctions are found. The exact factorized potential preserves the symmetry breaking effect when the coupling mode is present. Additionally the nodeless wavefunctions are found to be closely related to the adiabatic nuclear eigenfunctions. This phenomenon holds even for the regime where the non-adiabatic coupling is relevant, and sheds light on the relation between the exact wavefunction factorization and the adiabatic approximation.

The multi-layer multi-configuration time-dependent Hartree method (ML-MCTDH) is a highly efficient scheme for studying the dynamics of high-dimensional quantum systems. Its use is greatly facilitated if the Hamiltonian of the system possesses a particular structure through which the multi-dimensional matrix elements can be computed efficiently. In the field of quantum molecular dynamics, the effective interaction between the atoms is often described by potential energy surfaces (PES), and it is necessary to fit such PES into the desired structure. For high-dimensional systems, the current approaches for this fitting process either lead to fits that are too large to be practical, or their accuracy is difficult to predict and control. This article introduces multi-layer Potfit (MLPF), a novel fitting scheme that results in a PES representation in the hierarchical tensor (HT) format. The scheme is based on the hierarchical singular value decomposition, which can yield a near-optimal fit and give strict bounds for the obtained accuracy. Here, a recursive scheme for using the HT-format PES within ML-MCTDH is derived, and theoretical estimates as well as a computational example show that the use of MLPF can reduce the numerical effort for ML-MCTDH by orders of magnitude, compared to the traditionally used Potfit representation of the PES. Moreover, it is shown that MLPF is especially beneficial for high-accuracy PES representations, and it turns out that MLPF leads to computational savings already for comparatively small systems with just four modes., Comment: Copyright (2014) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics

A time-dependent approach for the kinetic energy release (KER) spectrum is developed for a fragmentation of a diatomic molecule after an electronic decay process, e.g. Auger process. It allows one to simulate the time-resolved spectra and provides more insight into the molecular dynamics than the time-independent approach. Detailed analysis of the time-resolved emitted electron and KER spectra sheds light on the interrelation between wave packet dynamics and spectra., Comment: This article has been modified and the newest version can be found in (J. Chem. Phys. 136, 114111 (2012)) at (http://link.aip.org/link/?JCP/136/114111). Copyright (2012) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics

In an electronic decay process followed by fragmentation the kinetic energy release and electron spectra can be measured. Classically they are the mirror image of each other, a fact which is often used in practice. Quantum expressions are derived for both spectra and analyzed. It is demonstrated that these spectra carry complementary quantum information and are related to the nuclear dynamics in different participating electronic states. Illustrative examples show that the classical picture of mirror image can break down and shed light on the underlying physics.