15 research outputs found
Semi-Empirical Haken-Strobl Model for Molecular Spin Qubits
Understanding the physical processes that determine the relaxation
and dephasing times of molecular spin qubits is critical for envisioned
applications in quantum metrology and information processing. Recent spin-echo
measurements of solid-state molecular spin qubits have stimulated the
development of quantum mechanical models for predicting intrinsic spin qubit
timescales using first-principles electronic structure methods. We develop an
alternative semi-empirical approach to construct Redfield quantum master
equations for molecular spin qubits using a stochastic Haken-Strobl model for a
central spin with a fluctuating gyromagnetic tensor due to spin-lattice
interaction and a fluctuating local magnetic field due to interactions with
other lattice spins. Using a vanadium-based spin qubit as a case study, we
compute qubit population and decoherence timescales as a function of
temperature and magnetic field using a bath spectral density parametrized with
a small number of measurements. The theory quantitatively agrees with
experimental data over a range of conditions beyond those used to parametrize
the model, demonstrating the generalization potential of the method. The
ability of the model to describe the temperature dependence of the ratio
is discussed and possible applications for designing novel
molecule-based quantum magnetometers are suggested.Comment: 7 pages, 5 figure
Model reduction for molecular diffusion in nanoporous media
Porous materials are widely used for applications in gas storage and
separation. The diffusive properties of a variety of gases in porous media can
be modeled using molecular dynamics simulations that can be computationally
demanding depending on the pore geometry, complexity and amount of gas
adsorbed. We explore a dimensionality reduction approach for estimating the
self-diffusion coefficient of gases in simple pores using Langevin dynamics,
such that the three-dimensional (3D) atomistic interactions that determine the
diffusion properties of realistic systems can be reduced to an effective
one-dimensional (1D) diffusion problem along the pore axis. We demonstrate the
approach by modeling the transport of nitrogen molecules in single-walled
carbon nanotubes of different radii, showing that 1D Langevin models can be
parametrized with a few single-particle 3D atomistic simulations. The reduced
1D model predicts accurate diffusion coefficients over a broad range of
temperatures and gas densities. Our work paves the way for studying the
diffusion process of more general porous materials as zeolites or
metal-organics frameworks with effective models of reduced complexity.Comment: 8 pages, 6 figure
First-Principles Screening of Metal-Organic Frameworks for Entangled Photon Pair Generation
The transmission of strong laser light in nonlinear optical materials can
generate output photons sources that carry quantum entanglement in multiple
degrees of freedom, making this process a fundamentally important tool in
optical quantum technology. However, the availability of efficient optical
crystals for entangled light generation is severely limited in terms of
diversity, thus reducing the prospects for the implementation of
next-generation protocols in quantum sensing, communication and computing. To
overcome this, we developed and implemented a multi-scale first-principles
modeling technique for the computational discovery of novel nonlinear optical
devices based on metal-organic framework (MOF) materials that can efficiently
generate entangled light via spontaneous parametric down-conversion(SPDC).
Using collinear degenerate type-I SPDC as a case study, we computationally
screen a database of 114,373 synthesized MOF materials to establish
correlations between the structure and chemical composition of MOFs with the
brightness and coherence properties of entangled photon pairs. We identify a
subset of 49 non-centrosymmetric mono-ligand MOF crystals with high chemical
and optical stability that produce entangled photon pairs with intrinsic
correlation times fs and pair generation rates in
the range smWmm at 1064 nm. Conditions for
optimal type-I phase matching are given for each MOF and relationships between
pair brightness, crystal band gap and optical birefringence are discussed.
Correlations between the optical properties of crystals and their constituent
molecular ligands are also given. Our work paves the way for the computational
design of MOF-based devices for optical quantum technology.Comment: Supplementary Material (13 pages, 12 figures, 2 table) at the end of
manuscript. Github (https://github.com/snoozynooj/Type-I-SPDC). arXiv admin
note: text overlap with arXiv:1807.10885 by other author
Multiscale structural control of linked metalâorganic polyhedra gel by aging-induced linkage-reorganization
Assembly of permanently porous metalâorganic polyhedra/cages (MOPs) with bifunctional linkers leads to soft supramolecular networks featuring both porosity and processability. However, the amorphous nature of such soft materials complicates their characterization and thus limits rational structural control. Here we demonstrate that aging is an effective strategy to control the hierarchical network of supramolecular gels, which are assembled from organic ligands as linkers and MOPs as junctions. Normally, the initial gel formation by rapid gelation leads to a kinetically trapped structure with low controllability. Through a controlled post-synthetic aging process, we show that it is possible to tune the network of the linked MOP gel over multiple length scales. This process allows control on the molecular-scale rearrangement of interlinking MOPs, mesoscale fusion of colloidal particles and macroscale densification of the whole colloidal network. In this work we elucidate the relationships between the gel properties, such as porosity and rheology, and their hierarchical structures, which suggest that porosity measurement of the dried gels can be used as a powerful tool to characterize the microscale structural transition of their corresponding gels. This aging strategy can be applied in other supramolecular polymer systems particularly containing kinetically controlled structures and shows an opportunity to engineer the structure and the permanent porosity of amorphous materials for further applications
SSAGES : Software Suite for Advanced General Ensemble Simulations
Molecular simulation has emerged as an essential tool for modern-day research, but obtaining proper results and making reliable conclusions from simulations requires adequate sampling of the system under consideration. To this end, a variety of methods exist in the literature that can enhance sampling considerably, and increasingly sophisticated, effective algorithms continue to be developed at a rapid pace. Implementation of these techniques, however, can be challenging for experts and non-experts alike. There is a clear need for software that provides rapid, reliable, and easy access to a wide range of advanced sampling methods and that facilitates implementation of new techniques as they emerge. Here we present SSAGES, a publicly available Software Suite for Advanced General Ensemble Simulations designed to interface with multiple widely used molecular dynamics simulations packages. SSAGES allows facile application of a variety of enhanced sampling techniquesâincluding adaptive biasing force, string methods, and forward flux samplingâthat extract meaningful free energy and transition path data from all-atom and coarse-grained simulations. A noteworthy feature of SSAGES is a user-friendly framework that facilitates further development and implementation of new methods and collective variables. In this work, the use of SSAGES is illustrated in the context of simple representative applications involving distinct methods and different collective variables that are available in the current release of the suite. The code may be found at: https://github.com/MICCoM/SSAGES-public
Strong influence of the H<sub>2</sub> binding energy on the MaxwellâStefan diffusivity in NU-100, UiO-68 and IRMOF-16
Molecular dynamics simulations of H2 at 243 K in NU-100, UiO-68 and IRMOF-16 with zero, one, three and six Mg alkoxide functional groups per linker were performed, revealing interesting behavior of the Maxwell-Stefan (M-S) diffusivity in these systems. A strong relationship between the isosteric heat of adsorption and the M-S diffusivity was found, with the M-S diffusivity decreasing exponentially with increasing heat of adsorption. The insights obtained may be valuable for future studies of diffusion and gas storage in nanoporous materials with strongly interacting functional groups
Machine learning identification of organic compounds using visible light
Identifying chemical compounds is essential in several areas of science and
engineering. Laser-based techniques are promising for autonomous compound
detection because the optical response of materials encodes enough electronic
and vibrational information for remote chemical identification. This has been
exploited using the fingerprint region of infrared absorption spectra, which
involves a dense set of absorption peaks that are unique to individual
molecules, thus facilitating chemical identification. However, optical
identification using visible light has not been realized. Using decades of
experimental refractive index data in the scientific literature of pure organic
compounds and polymers over a broad range of frequencies from the ultraviolet
to the far-infrared, we develop a machine learning classifier that can
accurately identify organic species based on a single-wavelength dispersive
measurement in the visible spectral region, away from absorption resonances.
The optical classifier proposed here could be applied to autonomous material
identification protocols or applications.Comment: 18 pages, 7 figures. Open database and python code. Version adds
comparison with Raman classifiers (Table 1
Understanding correlation between structure and entangled photon pair properties with metal-organic frameworks
Spontaneous parametric down conversion (SPDC) is a quantum second-order non- linear optical process where the photons generated are frequently used in quantum information processing. Materials with large second-order nonlinearities (Ï(2)) can be used as entangled photon sources with high brightness. The source brightness scales as the square of the effective nonlinearity (deff ) which is an intrinsic property of the mate- rial. Understanding material factors which can significantly alter this intrinsic property is useful in developing new materials which are SPDC efficient. In our work, we focus on understanding factors affecting the entangled photon pair properties such as the arrangements of ligands within the Zn(3-ptz)3 metal-organic framework (MOF) crystal and temperature. We find that the arrangement and alignment of the pyridine rings in the crystal structure significantly affect the deff and birefringence (ân). Smaller pyri- dine ring alignments relative to the optic c-axis increases the ân, which in turn leads to larger photon pair correlation times (Ïc) in coincidence measurements. Our work has significant implication in understanding the effect of ligand arrangement on deff and Ïc for any MOF crystal structure, providing a tool to rationalize the optimization of MOF crystals for the development of efficient nonlinear optical devices
Continuous fractional component Monte Carlo simulations of high-density adsorption in metalâorganic frameworks
<div><p>The continuous fractional component Monte Carlo method, which was designed to overcome difficulties with insertions and deletions of molecules, is modified to include configurational bias Monte Carlo methods and is further extended to binary systems. The modified method is shown to correctly predict adsorption of Ar in silicalite, Xe and Kr in HKUST-1, and enantiomers in a homochiral metalâorganic framework. The modified method is also found to be approximately an order of magnitude more efficient in inserting and deleting molecules than traditional configurational bias grand canonical Monte Carlo simulations in dense systems.</p></div
Pore-networked membrane for trace-level molecular separations in environmental water
The wide presence of pharmaceuticals and personal care products (PPCPs) in water is a major concern regarding current emerging pollution and urges their selective monitoring to establish water quality management. Microporous materials have been developed to extract organic contaminants and further embedded as fillers into polymeric composites like matrix-mixed membranes (MMMs) for practical use. Considering the relatively large molecular size of PPCPs and their slow diffusion in the membrane, the MMM configuration is, however, inadequate for liquid-phase separations. Here we report pore-networked membranes (PNMs) based on the concept of interconnecting the microporous fillers within the polymer matrix to form a continuous porous phase. Linked metal-organic polyhedra (MOP) network is designed for the continuous porous phase with tunable micro/mesopores, which are accessible for big PPCP molecules to facilitate their diffusion and adsorption. By contrast to MMMs, PNMs show enhanced stability, capacity and extraction selectivity towards specific pharmaceutical drugs amongst 13 PPCPs in environmental water matrices at trace-level concentrations