Rotational Constants Research Articles

Simulation of oriented NMR spectra: Combining molecular dynamics and chemical shift tensor calculations.

Solid state NMR is widely used to study the orientation and other structural features of proteins and peptides in lipid bilayers. Using data obtained by PISEMA (Polarization Inversion Spin Exchange at Magic Angle) experiments, periodic spectral patterns arise from well-aligned α-helical molecules. Significant problems in the interpretation of PISEMA spectra may arise for systems that do not form perfectly defined secondary structures, like α-helices, or the signal pattern is disturbed by molecular motion. Here, we present a new method that combines molecular dynamics simulation with tensorial orientational constraints (MDOC) and chemical shift tensor calculations for the simulation and interpretation of PISEMA-like spectra. The calculations include the spectra arising from non α-helical molecules and molecules with non-uniform intrinsic mobility. In a first step, dipolar or quadrupolar interaction tensors drive molecular rotations and reorientations to obtain the proper mean values as observed in corresponding NMR experiments. In a second step, the coordinate snapshots of the MDOC simulations are geometry optimized with the isotropic 15 N chemical shifts as constraints using Bond Polarization Theory (BPT) to provide reliable 15 N CS tensor data. The averaged dipolar 1 H-15 N couplings and the δzz tensor components can then be combined to simulate PISEMA patterns. We apply this method to the ß-helical peptide gramicidin A (gA) and demonstrate that this method enables the assignment of most PISEMA resonances. In addition, MDOC simulations provide local order parameters for the calculated sites. These local order parameters reveal large differences in backbone mobility between L- and D-amino acids of gA.

RotGT-2023: A benchmark data set of rotational g tensors.

The largest ever set, RotGT-2023, of statistically validated experimental components of rotational g tensors and respective vibrational corrections, has been created. The experimental values were collected from literature data. The vibrational corrections for obtaining equilibrium molecular g values have been calculated at the highest affordable coupled cluster level of theory. The set comprises 278 parameters from 129 molecules, including their isotopologues. Statistical assessment of the data has been performed to exclude unreliable parameters. A benchmarking of two theoretical approximations, based on coupled cluster and density functional theories, has been performed. The determined weighted mean and weighted standard deviations of the relative errors in calculated equilibrium g values are 1.09% and 2.07% for the ae-CCSD(T)/x2c-TZVPPall-s//ae-CCSD(T)/cc-pwCVTZ level. The obtained results can be used for predicting the rotational Zeeman effect, correcting rotational constants in spectroscopic studies and in molecular structure refinements. The latter has been demonstrated on the refinement of the molecular structure of silane SiH4, which resulted in rese(Si-H) = 1.473 323 1(27) Å. The other tested theoretical protocol, PBE0/x2c-TZVPPall-s//PBE0-D3BJ/def2-QZVPP, showed considerably worse statistical properties. The RotGT-2023 data set and the developed in this work statistical model are recommended for benchmarking of theoretical approximations for calculations of molecular magnetic properties.

Theoretical and Microwave Spectroscopic Characterization of Cyclobutenone: Planar or Puckered?

Cyclobutenone was characterized by high-resolution Fourier transform microwave spectroscopy for the first time. High-level, first-principles quantum chemical calculations at the B3LYP, CISD, MP2, and CCSD levels of theory were implemented to better understand the molecular structure and obtain model rotational and centrifugal distortion constants to aid in spectral assignment, and the results at the different levels of theory are compared. The assignment of the experimental spectrum provided fits of 2.7 kHz using Watson A-reduced and Watson S-reduced Hamiltonians. No tunneling splittings were observed, suggesting that cyclobutenone is not undergoing ring-puckering tunneling.

Nonlinear Dynamic Responses of Rigid Rotor Supported by Thick Top Foil Bearings

This study focuses on thick top foil bearings (TTFBs), which can prevent top foil from sagging and significantly reduce the load capacity of gas foil bearings (GFBs). However, the limited research on the dynamic responses of TTFB-rotor systems has hindered their wide application of TTFBs with high load capacity. To address this, an integrated nonlinear dynamic model is developed to analyze the linear dynamic responses of a rigid rotor supported on TTFBs. The model incorporates time domain orbit simulation, considering unsteady Reynolds equations, foil deformation equations, thick top foil motion equations, and rotor motion equations. A symmetrical test rig is used to validate the model, and three types of TTFBs with different bump foil stiffness are tested, with experimental results aligning with the model predictions. This study also investigates the effects of nominal clearance, static load, and unbalance on TTFB-rotor systems. The results indicate that unbalance has minimal impact on subsynchronous vibrations. However, larger bump foil stiffness, increased normal clearance, and higher static load contribute to improved stability and higher maximum stable speed of the TTFB-rotor system. Moreover, other relevant parameters reducing the bearing attitude angle can further enhance the system’s stability.

A computational and spectroscopic study of MgCCH (X2Σ+): towards characterizing MgCCH+

ABSTRACT New computational and experimental studies have been carried out for the MgCCH radical in its X2Σ+ state. Coupled cluster theory [CCSD(T)], was used in conjunction with post-CCSD(T) and scalar relativistic additive corrections to compute vibrational quartic force fields for MgCCH and its cation. From the quartic force fields, higher-order spectroscopic properties, including rotational constants, were obtained. In tandem, the five lowest energy rotational transitions for MgCCH, N = 1→0 through N = 5→4, were measured for the first time using Fourier transform microwave/millimetre wave methods in the frequency range 9–50 GHz. The radical was created in the Discharge Assisted Laser Ablation Source (DALAS) developed in the Ziurys group. A combined fit of these data with previous millimetre direct absorption measurements have yielded the most accurate rotational constants for MgCCH to date. The computed principle rotational constant lies within −1.51 to +1.65 MHz of the experimental one, validating the computational approach. High-level theory was then applied to produce rovibrational spectroscopic constants for MgCCH+, including a rotational constant of B0 = 5354.5–5359.5 MHz. These new predictions will further the experimental study of MgCCH+, and aid in the low-temperature characterisation of MgCCH in the interstellar medium.

The ground electronic state of ClF: Updated molecular constants and potential curves for 35ClF and 37ClF

A comprehensive assessment of available literature spectroscopic data and molecular constants for the X 1Σ+ ground electronic states of isotopologues 35ClF and 37ClF is undertaken. Three different approaches are employed in the analysis of the available information. The first approach involves merging molecular constants from various studies to yield an optimized set of Dunham coefficients {Y01, Y02, Y03, Y10, Y11, Y21, Y02 and Y12}. Utilizing these updated constants, vibrational energies (Gυ) and rotational constants (Bυ) for υ = 0–9 are calculated, and RKR potentials are determined for both isotopologues. The second approach involves calculating synthetic spectroscopic line positions using literature molecular constants, with normally distributed random errors added on, and subjecting these to a modern direct-potential-fit analysis. This analysis produces a precise analytical potential energy function for 35ClF, and Born-Oppenheimer breakdown functions that characterize adiabatic and non-adiabatic corrections. The third approach involves fitting the synthetic spectroscopic data directly to Dunham coefficients. The results of the three approaches are compared and discussed.

Thermochemistry of SinOx(OH)y Vapor Species from Quantum Chemical Calculations.

The thermochemistry of the Si-O-H system has been extensively studied both experimentally and theoretically due to its importance in chemical processes, degradation of silica-protected materials in combustion, and geological processes. In this paper, we review past studies and use quantum mechanical methods to generate a new data set. Molecular geometries were generated with DFT using the B3LYP functional. Energetics were calculated with RCCSD(T) methods extrapolated to the complete basis set (CBS/45) limit. Particular attention was given to the treatment of the vibrational modes. A rigid rotor model was used, corrections for anharmonicity were applied, and the Pitzer-Gwinn treatment of the hindered rotation of the M-OH groups was applied. The generated enthalpies of formation at 298 K are compared to those of experiments and other calculations. Generally, the agreement is good. A set of thermodynamic data (enthalpy of formation at 298 K, entropy at 298 K, and heat capacity polynomial to 3000 K) is presented for SiOH, SiO(OH), Si(OH)2, SiO(OH)2, Si(OH)3, Si(OH)4, Si2O(OH)6, and Si3O2(OH)8. These can be added to any of the common computational thermodynamics packages. The application of these data to high-temperature corrosion and geological problems is discussed.

Effect of equilibrium position offset on rotordynamics of a rigid rotor supported by hybrid foil magnetic bearings: Numerical and experimental investigations

This study investigates the influence of equilibrium position offset on the stability of a hybrid foil magnetic bearing (HFMB)-rotor system. Experimental tests and theoretical calculations are conducted using an established setup comprising the HFMB rotor system and a PID control system. The effects of equilibrium position offsets on resonance peaks, 1/2X subsynchronous vibration, and whip are analyzed through waterfall plots, synchronous vibration plots, rotor center orbit, and Fast Fourier transforms. The results reveal that the impact of equilibrium position offset on different vibration components varies due to distinct mechanisms of induced vibration. Surprisingly, the offset does not necessarily decrease system stability. Negative offset of the equilibrium position in the vertical direction mitigates tangential friction and 1/2X subsynchronous vibration. Conversely, positive offset of the equilibrium position in the vertical direction enhances system stiffness and the instability threshold of whip. These findings offer guidance for future PID controller designs for HFMBs and demonstrate the exceptional flexibility and controllability achievable with HFMBs.

The 130 – 750 GHz rotational spectrum of 2-cyanopyridine – Analysis of the ground vibrational state and the Coriolis-coupled dyad of its lowest-energy fundamental states

The millimeter-wave rotational spectrum of 2-cyanopyridine was collected from 130 to 750 GHz, and the ground and two lowest-energy excited vibrational states were analyzed. In total, over 20,000 rotational transitions were least-squares fit for the three vibrational states to partial-octic, distorted-rotor Hamiltonians with low error (σfit < 50 kHz). For the ground state, the many thousands of newly measured rotational transitions enabled substantial refinement of the rotational constants and determination of the centrifugal distortion constants. The rotational spectrum was collected at room temperature, permitting the observation of the two lowest-energy fundamental modes, ν30 (A″, 154 cm−1) and ν21 (A′, 175 cm−1), and determination of their spectroscopic constants. The two excited vibrational states are Coriolis coupled and require a two-state Hamiltonian. Eight Coriolis-coupling parameters (Ga,GaJ,GaK,GaJJ,Fbc,FbcJ,Gb,and GbJ) have been determined, as well as a precise energy difference of 26.524 312 6 (40) cm−1 between the vibrational states. A comparison of the ground-state spectroscopic constants, as well as the Coriolis coupling-related parameters of analogous dyads is presented for multiple cyanoarenes.

Ab initio interaction potentials of alkali metal (M = Na and K)–rare gas (Rg = He, Ne, Ar, Kr, Xe and Rn) complexes

Spectroscopic properties and potential energy curves of alkali metal (M = Na and K) – rare gas (Rg = He, Ne, Ar, Kr, Xe and Rn) van der Waals molecules in their ground states have been studied in detail using spin-restricted open-shell coupled cluster with single and double excitations and perturbative contribution of connected triple excitations (RCCSD(T)) methods. The core-valence correlation (CV) effect was found to be crucial for M-RG molecules containing heavy rare gas atoms. The electronic energies were corrected for the basis set superposition error (BSSE) using the counterpoise method. Energies were extrapolated to the complete basis set (CBS) limit using a two-point scheme. The permanent electric dipole moments, static electric dipole polarizabilities and long-range dispersion coefficients were also calculated. The computed spectroscopic constants, vibrational levels and rotational constants were reported for M-RG and good agreement with the available experimental and theoretical values were found.

Electrorheological effect of suspensions containing mixed size of poly(ionic liquid) microspheres

In this paper, the electrorheological (ER) effect of suspensions containing mixed size of poly(ionic liquid) (PIL) microspheres were studied by combining experiment and molecular dynamics simulation. The PIL microspheres with two particle sizes were prepared via a cooling-assisted phase separation method. The PIL microspheres were dispersed in silicone oil to form five kinds of suspensions with different volume ratios of large and small at a fixed particle volume fraction. The ER effect of these suspensions was measured by a rheometer. We established ER suspension models for five suspensions and simulated the rheological curves of the ER suspensions using molecular dynamics-stochastic rotation dynamics method. Both experiment and simulation results showed that the ER effect of suspensions containing mixed size of PIL microspheres was lower than that of suspensions containing uniform size of PIL microspheres. The reasons for the influence of mixed particle size on ER effect were analyzed through the three-dimensional visualization simulation results.

Characterizing the origin band spectrum of isoquinoline with resonance enhanced multiphoton ionization and electronic structure calculations.

We report the experimental resonance enhanced multiphoton ionization spectrum of isoquinoline between 315 and 310nm, along with correlated electronic structure calculations on the ground and excited states of this species. This spectral region spans the origin transitions to a π-π* excited state, which previous work has suggested to be vibronically coupled with a lower lying singlet n-π* state. Our computational results corroborate previous density functional theory calculations that predict the vertical excitation energy for the n-π* state to be higher than the π-π* state; however, we find an increase in the C-N-C angle brings the n-π* state below the energy of the π-π* state. The calculations find two out-of-plane vibrational modes of the n-π* state, which may be brought into near resonance with the π-π* state as the C-N-C bond angle increases. Therefore, the C-N-C bond angle may be important in activating vibronic coupling between the states. We fit the experimental rotational contour with a genetic algorithm to determine the excited state rotational constants and orientation of the transition dipole moment. The fits show a mostly in-plane polarized transition, and the projection of the transition dipole moment in the a-b plane is about 84° away from the a axis. These results are consistent with the prediction of our electronic structure calculations for the transition dipole moment of the π-π* excited state.

Theoretical study of amines containing molecules in the gas and water solvent

This study reports the infrared and electronic absorption spectra of amine-containing molecules. We investigate how these spectra differ for molecules in their neutral and ionic forms in gas and astrophysical H2O ice. Additionally, we analyze the pure rotational spectra of these molecules in the gas state. These are prebiotic molecules such as propargylamine (C3H5N), four isomers of C3H7N (1-aminopropene, 2-propenamine, allylamine, and cyclopropylamine), and two isomers of C3H9N (n-propyl amine and 2-aminpropane) considered for the study. We analyzed various properties of molecules in different states: gas phase, water solvent, and ionic states. We used the coupled-cluster method (CCSD) with a 6–311++G** basis set for our studies. The rotational constants obtained at this level of theory are well matching with the available experimental determinations. These constants are further used to calculate the rotational spectra and their transitions. The calculated vibrational frequencies of these molecules matched well with experimental results at this level of theory. To study the influence of solvent, we employed the IEFPCM model at the same level of theory. We used the equation of motion coupled cluster theory (EOM-CCSD) at the CCSD/6–311++G** level of theory to examine the electronic absorption spectra. We reported the HOMO-LUMO gap, electronic transitions, and oscillator strength of these transitions. We identified the best lines from microwave and infrared regions to observe these molecules in interstellar environments. All calculations were performed using the Gaussian 16 and PGOPHER program packages.

Precise Equilibrium Structure of Benzene.

Recent advances in gas-phase structure determination afford outstanding agreement between the CCSD(T)/cc-pCVTZ-corrected semi-experimental (reSE) equilibrium structures and their corresponding best theoretical estimates (BTEs) of the equilibrium structures (re) based upon corrections to the CCSD(T)/cc-pCV5Z geometries for the aromatic heterocycles pyrimidine and pyridazine. Herein, that same analysis is extended to the fundamental aromatic molecule benzene, using published experimental spectroscopic data for a total of 11 available isotopologues. The incorporation of rotational constants from all of these isotopologues and CCSD(T) corrections to address the impacts of both the vibration-rotation interaction and electron-mass distribution results in a highly precise and accurate reSE structure. The CCSD(T)/cc-pCV5Z optimized geometry has been further corrected to address a finite basis set, untreated electron correlation, relativistic effects, and a breakdown of the Born-Oppenheimer approximation. This analysis achieves outstanding agreement between the re (BTE) and reSE structural parameters of benzene to a highly satisfying level (0.0001 Å), an agreement that surpasses our recently published structures of the aforementioned nitrogen-substituted benzene analogues. The D6h geometry of benzene is now known to an unprecedented precision: RC-C = 1.3913 (1) Å and RC-H = 1.0809 (1) Å. The mutual agreement between theory and experiment presented in this work validates both, substantially resolving all discrepancies between the reSE and theoretical re structures available in the literature.

Attachment of Hydrogen Molecules to Atomic Ions (Na+, Cl-): Examination of an Adiabatic Separation of the H2 Rotational Motion.

Interactions between molecular hydrogen and ions are of interest in cluster science, astrochemistry and hydrogen storage. In dynamical simulations, H2 molecules are usually modelled as point particles, an approximation that can fail for anisotropic interactions. Here, we apply an adiabatic separation of the H2 rotational motion to build effective pseudoatom-ion potentials and in turn study the properties of (H2)nNa+/Cl- clusters. These interaction potentials are based on high-level ab initio calculations and Improved Lennard-Jones parametrizations, while the subsequent dynamics has been performed by quantum Monte Carlo calculations. By comparisons with simulations explicitly describing the molecular rotations, it is concluded that the present adiabatic model is very adequate. Interestingly, we find differences in the cluster stabilities and coordination shells depending on the spin isomer considered (para- or ortho-H2), especially for the anionic clusters.

Fuzzy variable gain robust control of active magnetic bearings rigid rotor system

AbstractA high speed rigid rotor system supported by active magnetic bearings (AMBs) puts forward higher requirements on the performance of controllers. The fuzzy variable gain H‐infinity robust control (FVGRC) method is proposed to simplify controller design while suppressing system uncertainty. First, the T‐S fuzzy model of four‐degree‐of‐freedom (4‐DOF) AMBs was established based on the 4‐DOF AMBs rigid rotor equivalent coupling model optimised by the μ‐gap metric. Then, based on the fuzzy models of AMBs systems under different operating conditions, the relative optimal weight function value of H‐infinity robust controller was calculated when AMBs system was at value of the speed endpoint, and the fuzzy variable gain H‐infinity robust (FVGR) controller was designed on this basis. Finally, the simulation and experimental results showed that the FVGRC can simplify the model of controller and ensure the stable operation of AMBs rigid rotor system in the full speed range under high‐speed conditions.

Hydrogen-Bonded Polymer Nanomedicine with AIE Characteristic for Intelligent Cancer Therapy.

One of the major goals of biomedical science is to pioneer advanced strategies toward precise and smart medicine. Hydrogen-bonding (H-bonding) assembly incorporated with an aggregation-induced emission (AIE) capability can serve as a powerful tool for developing supramolecular nanomedicine with clear tumor imaging and smart therapeutic performance. We here report a H-bonded polymeric nanoformulation with an AIE characteristic toward smart antitumor therapy. To do so, we first design a structurally novel tetraphenylethylene (TPE)-based H-bonding theranostic prodrug, TPE-(FUA)4, characterized by four chemotherapeutic fluorouracil-1-acetic acid (FUA) moieties arched to the TPE core. A six-arm star-shaped amphiphilic polymer vehicle, P(DAP-co-OEGEA)6, is prepared, bearing hydrophilic and biocompatible POEGEA (poly(oligo (ethylene glycol) ethyl acrylate) segments, along with a hydrophobic and H-bonding PDAP (poly(diaminopyridine acrylamide)) segment. Thanks to the establishment of the DAP/FUA H-bonding association, incorporating the TPE-(FUA)4 prodrug to the P(DAP-co-OEGEA)6 vehicle can yield H-bond cross-linked nanoparticles with interpenetrating networks. For the first time, AIE luminogens are interwoven into a six-arm star-shaped polymer via an intrinsic H-bonding array of the chemotherapeutic agent FUA, thus imposing an effective restriction of TPE molecular rotations. Concomitantly, encapsulated photothermal agent (IR780) via a hydrophobic interaction facilitates the formation of nanoassemblies, TPE-(FUA)4/IR780@P(DAP-co-OEGEA)6, featuring synergistic cancer chemo/photothermal therapy (CT/PTT). Our study can contribute a practical solution to fulfill biomedical requirements with a conductive advance in precision nanomedicine.

Analysis of the effect of the translational-rotational coupling on the pseudo-diffusion along the molecular axes of meta-cresol: A molecular dynamics analysis

We investigate the dynamical properties (translation and rotation) of the glass-forming liquid meta-cresol by molecular dynamics simulations. This system is investigated at 9 temperatures between 230 K and 400 K, encompassing the liquid and glassy states of meta-cresol. In order to get insight into the coupling between the translational and rotational motions, the centre of mass velocity autocorrelation function is calculated along the principal axes of meta-cresol. We show that the time behaviour of the velocity and angular velocity is connected to the change in the local structure occurring upon the glass transition. Indeed, the long-time negative region in the velocity autocorrelations is associated with a caging effect while the occurrence of a short time negative region in these functions is considered as a signature of hydrogen bonding interactions. By studying, the centre of mass velocity of meta-cresol in the molecular frame, the translation and rotation coupling was directly evidenced. The time evolution of the translational-rotational coupling is evaluated from the difference ΔαRTC(t) between the velocity autocorrelation function calculated with respect to the molecular frame (where α stands for the three axes of the local cartesian frame fixed to the individual molecule, x, y, and z) of the meta-cresol molecule and that of the same function calculated in the frame of the hypothesis that there is no statistical correlation between the translational and rotational motions. The positive regions of ΔαRTC(t) indicate an occurrence of a cooperative effect, which means that the each of the two motions is realized in the favour of the other. Conversely, negative regions indicate that the rotation and translation motions are anti-cooperative. Our results show that a strong coupling between translation and rotation occurs along the × axis that is perpendicular to the ring of meta-cresol molecule, and also along which the hydrogen bond is established.

Structure, Frontier Molecular Orbitals, MEP, Charge Analysis, and NLO Study of 2,4-, 2,5-, and 2,6-Dimethylanilines Using DFT

This study includes the evaluation of most stable structure, frontier molecular orbitals, molecular electrostatic potential (MEP), and nonlinear optical (NLO) parameters of 2,4-dimethylaniline (2,4DMA), 2,5-dimethylaniline (2,5DMA), and 2,6-dimethylaniline (2,6DMA) using density functional theory (DFT) employing B3LYP functional with 6-311++G(d,p) basis set. HOMO-LUMO energies, band gap energies, and global reactivity descriptors were obtained from the optimized structures. The band gap energy was determined as 3.7865, 3.9348, and 3.9443 eV for 2,4DMA, 25DMA, and 2,6DMA, respectively. The reactive sites of the molecules were obtained from the molecular electrostatic potential energy. The NLO parameters such as dipole moment, polarizability, and hyperpolarizability have been investigated for the title molecules. The investigated dipole moment and first-order hyperpolarizability values are higher than the prototypical value of urea and show good NLO behavior. The NMR chemical shifts, electronic absorption spectra, and charge distribution of atoms were calculated theoretically. Furthermore, thermodynamic and rotational constants were also calculated.

Noncovalent Interactions in the Molecular Geometries of 4-Methylthiazole···H2O and 5-Methylthiazole···H2O Revealed by Microwave Spectroscopy.

The pure rotational spectra of 4-methylthiazole···H2O and 5-methylthiazole···H2O were recorded by chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. Each complex was generated within the rotationally cold environment of a gas sample undergoing supersonic expansion in the presence of an argon buffer gas. The spectra of five isotopologues of each complex have been measured and analyzed to determine the rotational constants, A0, B0, and C0; centrifugal distortion constants, DJ, DJK, and d1; nuclear quadrupole coupling constants, χaa(N3) and [χbb(N3) - χcc(N3)]; and parameters describing the internal rotation of the CH3 group, V3 and ∠(i,b). The experimentally deduced parameters were obtained using the XIAM and the BELGI-Cs-hyperfine code. For each complex, parameters in the molecular geometry are fitted to experimentally determined moments of inertia. DFT calculations have been performed at the ωB97X-D/aug-cc-pVQZ level in support of the experiments. Each complex contains two hydrogen bonds; a comparatively strong, primary interaction between the N of thiazole and an O-H of H2O, and a weaker, secondary interaction between O and either the hydrogen atom attached to C2 (in 5-methylthiazole···H2O) or the CH3 group attached to C4 (in 4-methylthiazole···H2O). The barrier to internal rotation of the CH3 group, V3, is slightly lower for 4-methylthiazole···H2O (XIAM result is 340.05(56) cm-1) than that for the 4-methylthiazole monomer (357.6 cm-1). This is likely to be a result of internal charge redistribution within the 4-methylthiazole subunit following its coordination by H2O. At the precision of the experiments, V3 of 5-methylthiazole···H2O (XIAM result is 325.16(38) cm-1) is not significantly different from V3 of the 5-methylthiazole monomer (332.0 cm-1).