Quadrupole Coupling Research Articles

Stretch-Induced Ordering of Prochiral Dimethyl Sulfoxide in Anisotropic Hydrogels Analysed by 1H and 2H Nuclear Magnetic Resonance.

Nuclear spins in small molecules dissolved in stretched hydrogels typically have population-averaged residual interactions. The nuclear magnetic resonance (NMR) spectra of these systems often show additional peaks and splittings compared with free solutions. Residual dipolar couplings (RDCs) and quadrupolar couplings (RQCs) are observed for guest1H or2H nuclear spins, respectively. Dimethyl sulfoxide (DMSO) is an exquisitely sensitive probe of such biologically relevant environments since it is prochiral and becomes effectively chiral when embedded in anisotropic gelatin-based hydrogels. Measured1H RDCs and2H RQCs were used to estimate bond order parametersover a wide range of stretching extents.At the largest extent of stretching, the2H splittings were-73.0 and-9.4 Hz, similar to those found for guest molecules in liquid crystals. Inhomogeneous line broadening of the2H resonances was related to the size of the RQC due to a spatial distribution of RQCs, which was revealed using a one-dimensional slice selective imaging experiment along the stretching direction.1H NMR spectra exhibited homogeneous line broadening, with resonance integrals that indicated concealed multiplet structure. Understanding molecular bond ordering in mechanically oriented environments provides a conceptual framework for investigating more complex systems including zeolites and those foundin vivo.

XIAM-NQ: Implementation of exact quadrupole coupling

In rotational spectroscopy, the nuclear quadrupole coupling of spins to the rotation of a molecule frequently leads to significant hyperfine splittings of spectral lines, complicating spectral analysis. This complexity increases further when internal rotation fine splittings, particularly from methyl groups, are also present. The XIAM program, recognized in the community for its ability to address methyl internal rotation and handle nuclear quadrupole coupling for a single nucleus, while neglecting off-diagonal matrix elements in the quantum number J, has now been enhanced. The updated version, XIAM-NQ, includes the previously omitted matrix elements, enabling an exact treatment of quadrupole coupling. This new version offers precise spectral fits with minimal fitting times, even for molecules containing bromine and iodine nuclei. The effectiveness of XIAM-NQ is demonstrated on o-halotoluenes and m-chlorotoluene.

Isotopic species, vibrational states and nuclear quadrupole splitting in CH[formula omitted]Cl[formula omitted] from rotational spectroscopy at 8–18 GHz

The present work fills several significant gaps in the study of the rotational spectrum of the methylene chloride molecule. Two Fourier transform microwave spectrometers were used, providing complementary coverage of the 8–18 GHz region, at room temperature and in supersonic expansion. Hyperfine resolved measurements were made and fitted for ground states of the CH235Cl2, CH235Cl37Cl, CH237Cl2, and 13CH235Cl2 isotopic species, as well as for nine different excited vibrational states. Transitions in the v4=2, v4=3, v3=1, v9=1 states in CH235Cl2, and transitions in excited states of the ν4 mode in 35Cl37Cl and 37Cl2 isotopic species have been assigned for the first time. Vibrational and isotopic dependence of nuclear quadrupole coupling constants was identified. The v3=1 and v9=1 states in CH235Cl2 were found to be significantly coupled by c-axis Coriolis interaction, while transitions in v4=2 and v4=3 states exhibited hyperfine mediated perturbations enhancing the determination of the χab parameter and allowing assessment of its vibrational dependence.

Molecular influence on nuclear-quadrupole-coupling effects in laser induced alignment.

We computationally studied the effect of nuclear-quadrupole interactions on the field-free impulsive alignment of different asymmetric-top molecules. Our analysis is focused on the influence of the hyperfine- and rotational-energy-level structures. These depend on the number of nuclear spins, the rotational constants, and the symmetry of the tensors involved in the nuclear spin and external field interactions. Comparing the prototypical large-nuclear-spin molecules iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, and 2,5-diiodobenzonitrile, we demonstrate that the magnitude of the hyperfine splittings compared to the rotational-energy splittings plays a crucial role in the spin-rotational dynamics after the laser pulse. Moreover, we point out that the impact of the quadrupole coupling on the rotational dynamics decreases when highly excited rotational states dominate the dynamics.

Microwave spectrum and molecular structure calculations for η4-butadiene ruthenium tricarbonyl

The microwave spectrum of η4-butadiene ruthenium tricarbonyl was measured in the 5–15 GHz frequency range using a Flygare-Balle type pulsed beam Fourier transform microwave (FTMW) spectrometer. The rotational constants for the 102Ru isotopologue were determined to have the following values: A = 932.20099(42), B = 858.03248(47) and C = 831.35161(37) MHz. The centrifugal distortion constant dJ is 0.0862(29)kHz. 22 a-dipole and 4c-dipole transitions were measured. Extensive high-level G16 calculations were made using DFT and MP2 methods with various basis sets, some including core-potentials (ECP). The best structure was calculated with Gaussian 16 using B3LYP/def2-QZVPP, which includes a core potential (ECP). Extensive all-electron calculations were made based on the best ECP structure to predict 101Ru and 99Ru quadrupole coupling strengths. Quadrupole hyperfine structure splittings were measured for both 101Ru and 99Ru. The hyperfine structure splittings for the 101Ru nuclear quadrupole were measured, yielding the values of 1.5χaa = 98.12(17) MHz and 0.25(χbb-χcc) = 36.059(30). Measured hyperfine structure splittings for 99Ru quadrupole coupling yielded the values of 1.5χaa = 16.99(77) MHz and 0.25(χbb-χcc) = 6.23(32). These values are in reasonable agreement with some of the all-electron calculations.

Geometry of the argon…imidazole complex revealed by the microwave spectra of four isotopologues

The rotational spectra of four isotopologues of an isolated complex formed between an argon atom and imidazole, Ar…imidazole, have been recorded in the 6–19 GHz region by Fourier transform microwave spectroscopy. Rotational transition frequencies have been fitted to Watson’s S-reduced Hamiltonian to yield rotational, centrifugal distortion and nuclear quadrupole coupling constants for the complex. Rotational constants determined for the parent and three 15N-containing isotopologues allow the three-dimensional structure of the complex to be described. The two angles, θ and ϕ, which define the orientation of the Ar atom relative to the imidazole ring have been determined for the first time in addition to the distance between Ar and the center of mass of the imidazole sub-unit, R. Fitting of structural parameters to the experimentally-determined moments of inertia yields a structure where Ar is positioned above the ring plane at a distance of 3.519 Å from the center of mass of the imidazole sub-unit. In the experimentally determined, average geometry, the intermolecular axis (drawn through Ar and the center of mass of the imidazole sub-unit) is oriented at 6° from the normal to the ring plane. The experimental results allow for four alternative possibilities for ϕ with 62.0(39)° being that which is most consistent with expectations for this parameter based on previous work. The experimentally-determined nuclear quadrupole coupling constants imply that the electric field gradient at each of the nitrogen nuclei of imidazole does not significantly change on formation of the complex with Ar.

Quadrupole Coupling of Circular Rydberg Qubits to Inner Shell Excitations.

Divalent atoms provide excellent means for advancing control in Rydberg atom-based quantum simulation and computing due to the second optically active valence electron available. Particularly promising in this context are circular Rydberg atoms, for which long-lived ionic core excitations can be exploited without suffering from detrimental autoionization. Here, we report the implementation of electric quadrupole coupling between the metastable 4D_{3/2} level and a very high-n (n=79) circular Rydberg qubit, realized in doubly excited ^{88}Sr atoms prepared from an optical tweezer array. We measure the kHz-scale differential level shift on the circular Rydberg qubit via beat-node Ramsey interferometry comprising spin echo. Observing this coupling requires coherent interrogation of the Rydberg states for more than 100 μs, which is assisted by tweezer trapping and circular state lifetime enhancement in a black-body radiation suppressing capacitor. Further, we find no noticeable loss of qubit coherence under continuous photon scattering on the ion core, paving the way for laser cooling and imaging of Rydberg atoms. Our results demonstrate access to weak electron-electron interactions in Rydberg atoms and expand the quantum simulation toolbox for optical control of highly excited circular state qubits via ionic core manipulation.

Structural and Electronic Evolution of Ethanolamine upon Microhydration: Insights from Hyperfine Resolved Rotational Spectroscopy

AbstractEthanolamine hydrates containing from one to seven water molecules were identified via rotational spectroscopy with the aid of accurate quantum chemical methods considering anharmonic vibrational corrections. Ethanolamine undergoes significant conformational changes upon hydration to form energetically favorable hydrogen bond networks. The final structures strongly resemble the pure (H2O)3–9 complexes reported before when replacing two water molecules by ethanolamine. The 14N nuclear quadrupole coupling constants of all the ethanolamine hydrates have been determined and show a remarkable correlation with the strength of hydrogen bonds involving the amino group. After addition of the seventh water molecule, both hydrogen atoms of the amino group actively contribute to hydrogen bond formation, reinforcing the network and introducing approximately 21–27 % ionicity towards the formation of protonated amine. These findings highlight the critical role of microhydration in altering the electronic environment of ethanolamine, enhancing our understanding of amine hydration dynamics.

Structural and Electronic Evolution of Ethanolamine upon Microhydration: Insights from Hyperfine Resolved Rotational Spectroscopy.

Ethanolamine hydrates containing from one to seven water molecules were identified via rotational spectroscopy with the aid of accurate quantum chemical methods considering anharmonic vibrational corrections. Ethanolamine undergoes significant conformational changes upon hydration to form energetically favorable hydrogen bond networks. The final structures strongly resemble the pure (H2O)3-9 complexes reported before when replacing two water molecules by ethanolamine. The 14N nuclear quadrupole coupling constants of all the ethanolamine hydrates have been determined and show a remarkable correlation with the strength of hydrogen bonds involving the amino group. After addition of the seventh water molecule, both hydrogen atoms of the amino group actively contribute to hydrogen bond formation, reinforcing the network and introducing approximately 21-27 % ionicity towards the formation of protonated amine. These findings highlight the critical role of microhydration in altering the electronic environment of ethanolamine, enhancing our understanding of amine hydration dynamics.

Rotational spectroscopy and structure of 1,1-dichloro-1-silacyclohex-2-ene

The ground state rotational spectrum of 1,1-dichloro-1-silacyclohex-2-ene has been recorded using a chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer. Several isotopologues in their natural abundances have been observed in the free-jet expansion, and their spectra assigned, making it possible to present a partial heavy-atom substitution structure. Furthermore, the high resolution of this technique allows the complicated hyperfine splitting pattern to be largely deconvoluted. As a result, the on-diagonal nuclear quadrupole coupling constants for the two chlorine atoms have been determined for all observed isotopologues. Additionally, χbc is determined for both chlorine atoms of the parent species. The quadrupole coupling tensors for the parent species have been diagonalised, noting some assumptions have been made pertaining to the off-diagonal nuclear quadrupole coupling constants in the principal axis system, to yield reasonable values of χzz and η which are then compared.

Theoretical investigation of the effects of diverse hydrogen-bonding characteristics on the 17O chemical shielding and electric field gradient tensors within the active sites of MraYAA bound to nucleoside antibiotics capuramycin, carbacaprazamycin, 3′-Hydroxymureidomycin A, and muraymycin D2

This study builds upon our prior researches and seeks to investigate and clarify the influences of various characteristics of hydrogen bonds (H-bonds) and charge transfer (CT) interactions, which were detected within the inhibitor binding pockets (labeled as the QM models I–IV) of MraYAA–capuramycin, MraYAA–carbacaprazamycin, MraYAA–3′-hydroxymureidomycin A, and MraYAA–muraymycin D2 complexes by QTAIM and NBO analyses from DFT QM/MM MD calculations, on the 17O chemical shielding (CS) and electric field gradient (EFG) tensors of carboxylate (Oδ), carbonyl (C═O), and hydroxyl (O–H) oxygens in these models. The 17O CS and EFG tensors of these three types of oxygens in QM models I–IV were calculated at the M06-2X/6-31G** level by including the solvent effects using the polarizable continuum model. From the computed 17O CS and EFG tensors in these models, it was found that the nuclear shielding, σiso, for carboxylate or carbonyl oxygen increases (shielding effect) as the H-bond length decreases and the percentage p-character of nOδ/nC═O lone pair partner in the CT interaction enhances. In contrast, the σiso (17O–H) decreases (deshielding effect) with a reduction in the H-bond length as well as with an enhancement in percentage s-character of the nOH lone pair/σ*O–H antibond. By reducing the H-bond length or by increasing p-character of the nOδ/nC═O lone pair, the 17Oδ/17O═C quadrupole coupling constant smoothly decreases, while the 17Oδ/17O═C asymmetry parameter smoothly increases. Moreover, these calculated parameters are in a good agreement with the experimental values. The information garnered here is valuable particularly for further understanding of empirical correlations between 17O NMR spectroscopic and H-bonding characteristics in the protein–ligand complexes.

Higher-order tails and RG flows due to scattering of gravitational radiation from binary inspirals

We establish and develop a novel methodology to treat higher-order non-linear effects of gravitational radiation that is scattered from binary inspirals, which employs modern scattering-amplitudes methods on the effective picture of the binary as a composite particle. We spell out our procedure to study such effects: assembling tree amplitudes via generalized-unitarity methods and employing the closed-time-path formalism to derive the causal effective actions, which encompass the full conservative and dissipative dynamics. We push through to a new state of the art for these higher-order effects, up to the third subleading tail effect, at order GN5\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ {G}_N^5 $$\\end{document} and the 5-loop level, which corresponds to the 8.5PN order. We formulate the consequent dissipated energy for these higher-order corrections, and carry out a renormalization analysis, where we uncover new subleading RG flow of the quadrupole coupling. For all higher-order tail effects we find perfect agreement with partial observable results in PN and self-force theories, where available.

Electric Field Gradient Calculations for Ice VIII and IX Using Polarizable Embedding: A Comparative Study on Classical Computers and Quantum Simulators.

We test the performance of the polarizable embedding variational quantum eigensolver self-consistent field (PE-VQE-SCF) model for computing electric field gradients with comparisons to conventional complete active space self-consistent-field (CASSCF) calculations and experimental results. We compute quadrupole coupling constants for ice VIII and ice IX. We find close agreement of the quantum-computing PE-VQE-SCF results with the results from the classical PE-CASSCF calculations and with experiment. Furthermore, we observe that the inclusion of the environment is crucial for obtaining results that match the experimental data. The calculations for ice VIII are within the experimental uncertainty for both CASSCF and VQE-SCF for oxygen and lie close to the experimental value for ice IX as well. With the VQE-SCF, which is based on an adaptive derivative-assembled problem-tailored (ADAPT) ansatz, we find that the inclusion of the environment and the size of the different basis sets do not directly affect the gate counts. However, by including an explicit environment, the wavefunction and therefore the optimization problem become more complicated, which usually results in the need to include more operators from the operator pool, thereby increasing the depth of the circuit.

A Tale of Two Tails: Rotational Spectroscopy of N-Ethyl Maleimide and N-Ethyl Succinimide.

Broadband microwave spectra of N-ethyl maleimide (NEM) and N-ethyl succinimide (NES) have been recorded using chirped pulse Fourier transform microwave spectroscopy in the Ka-band (26.5-40 GHz). The spectra for both molecules were fit to a Watson A-reduced Hamiltonian in the Ir representation to obtain best fit experimental rotational constants (NEM: A0 = 2143.1988(29), B0 = 1868.7333(22), C0 = 1082.98458(36); NES: A0 = 2061.47756(14), B0 = 1791.73517(12), C0 = 1050.31263(11)), centrifugal distortion constants, and nuclear quadrupole coupling constants. While the heavy atoms of the five-membered ring of both molecules are planar, the ethyl chain has its terminal methyl group perpendicular to the ring. Along the relaxed potential energy curve for the ethyl dihedral angle (θ1 = C(6)-C(5)-N-C(4)), the ethyl group experiences significant steric strain when it is in the plane of the ring, associated with the interaction of the ethyl group with the two carbonyl oxygens. This leads to calculated barriers of θ1 = 1469 cm-1 and θ1 = 1680 cm-1 in N-ethyl maleimide and N-ethyl succinimide, respectively.

The Heavy Atom Structure, "cis effect" on Methyl Internal Rotation, and 14N Nuclear Quadrupole Coupling of 1-Cyanopropene from Quantum Chemical and Microwave Spectroscopic Analysis.

The microwave spectrum of 1-cyanopropene (crotonitrile) was remeasured using two pulsed molecular jet Fourier transform microwave spectrometers operating from 2.0 to 40.0 GHz. The molecule exists in two isomer forms, E and Z, with respect to the orientation between the methyl and the cyano groups. The spectrum of the Z isomer is more intense. Due to internal rotation of the methyl group, doublets containing A and E torsional species were found for all rotational transitions. Hyperfine splittings arising from the 14N nuclear quadrupole coupling were resolved. The heavy atom structure of the Z isomer was determined by observation of 13C and 15N isotopologue spectra in natural abundances. The experimental results were supported by quantum chemistry. The complex spectral patterns were analyzed and fitted globally, and the barriers to methyl internal rotation are determined to be 478.325(28) cm-1 and 674.632(76) cm-1 for the Z and E isomers, respectively. The non-bonded intramolecular electrostatic attraction between the methyl group and the 1-cyano substituent overcomes steric hindrance, leading to higher stability of the Z isomer. The consequence is a slight opening of 3.2° of the C(1)-C(2)-C(3) angle and a radical decrease of the methyl torsional barrier in the Z isomer due to steric repulsion.

Discovery of the interstellar cyanoacetylene radical cation HC3N+

We report the first identification in space of HC3N+, the simplest member of the family of cyanopolyyne cations. Three rotational transitions with half-integer quantum numbers from J = 7/2 to 11/2 have been observed with the Yebes 40 m radio telescope and assigned to HC3N+, which has an inverted 2Π ground electronic state. The three rotational transitions exhibit several hyperfine components due to the magnetic and nuclear quadrupole coupling effects of the H and N nuclei. We confidently assign the characteristic rotational spectrum pattern to HC3N+ based on the good agreement between the astronomical and theoretical spectroscopic parameters. We derived a column density of (6.0 ± 0.6)×1010 cm−2 and a rotational temperature of 4.5 ± 1 K. The abundance ratio between HC3N and HC3N+ is 3200 ± 320. As found for the larger members of the family of cyanopolyyne cations (HC5N+ and HC7N+), HC3N+ is mainly formed through the reactions of H2 and the cation C3N+ and by the reactions of H+ with HC3N. In the same manner than other cyanopolyyne cations, HC3N+ is mostly destroyed through a reaction with H2 and a dissociative recombination with electrons.

Electric nuclear quadrupole coupling reveals dissociation of HCl with a few water molecules

Investigating the dissociation of acids in the presence of a limited number of water molecules is crucial for understanding various elementary chemical processes. In our study, focusing on HCl(H 2 O) n clusters (where HCl is hydrogen chloride and H 2 O is water) formed in a cold and isolated jet expansion, we used the nuclear quadrupole coupling tensor obtained through rotational spectroscopy to decipher the nature of the hydrogen-chlorine (H-Cl) chemical bond in a microaqueous environment. For n = 1 to 4, the H-Cl bond is covalent. At n = 5 and 7, the contact ion pair of H 3 O + Cl − is spontaneously formed within the hydrogen bond networks of book and cube acid-water clusters, respectively.

A combined solid-state 1H, 13C, 17O NMR and periodic DFT study of hyperfine coupling tensors in paramagnetic copper(II) compounds

We report solid-state 1H, 13C, and 17O NMR determination of hyperfine coupling tensors (A-tensors) in several paramagnetic Cu(II) (d9, S = 1/2) complexes: trans-Cu(DL-Ala)2·H217O, Cu([1–13C]acetate)2·H2O, Cu([2–13C]acetate)2·H2O, and Cu(acetate)2·H217O. Using these new experimental results and some A-tensor data available in the literature for trans-Cu(L-Ala)2 and K2CuCl4·2H2O, we were able to examine the accuracy of A-tensor computation from a periodic DFT method implemented in the BAND program. We evaluated A-tensors on 1H (I = 1/2), 13C (I = 1/2), 14N (I = 1), 17O (I = 5/2), 39K (I = 3/2), 35Cl (I = 3/2), and 63Cu (I = 3/2) nuclei over a range spanning more than 3 orders of magnitude. We found that the BAND code can reproduce reasonably well the experimental results for both A-tensors and nuclear quadrupole coupling tensors.

Microwave spectroscopy and large amplitude motion of chlorosulfonic acid (ClSO2OH)

The high-resolution rotational spectrum of chlorosulfonic acid (ClSO2OH) has been studied using both broadband and cavity-based Fourier transform microwave spectrometers over the frequency range of 5–18 GHz. a-, b-, and c-type transitions have been recorded for both the 35Cl and 37Cl isotopologues. The observation of c-type lines establishes that the molecule lacks a plane of symmetry and suggests that the OH group can undergo large amplitude motion between equivalent structures. Interconversion between these structures can be achieved via internal rotation through two inequivalent barriers occurring at Cl-S-O-H torsional angles of 0 or 180degrees. As in previous work on triflic and methanesulfonic acids, two states are observed and are treated as tunneling states which are presumed to arise primarily due to motion through the lower of the two barriers. The a- and c-type transitions occur within each of these states while the b-type transitions cross between them. Rotational, centrifugal distortion, and chlorine nuclear quadrupole coupling constants, as well as the energy difference between the two tunneling states and associated coupling constants, have been determined. The experimental tunneling energies, ΔE, for the 35Cl and 37Cl isotopologues are 52.6926(16) MHz and 52.6397(46) MHz, respectively. Quantum chemical calculations were carried out using MP2 and B3LYP density functional theory (DFT) methods with an aug-cc-pVTZ basis set. The rotational constants from the optimized structures were in good agreement with the experimental values. The lowest energy barrier for OH motion was calculated to be 2.63 kcal/mol at the B3LYP/aug-cc-pVTZ level. The effects of the large amplitude motion are similar to those recently reported for triflic acid (CF3SO2OH) and methanesulfonic acid (CH3SO2OH). However, while the tunneling splittings in chlorosulfonic and triflic acids are virtually identical, they differ significantly from that of methanesulfonic acid.

Coupled internal rotations and 14N quadrupole hyperfine structure of 2,4-dimethylpyrrole investigated by microwave spectroscopy and quantum chemistry.

The microwave spectrum of 2,4-dimethylpyrrole was investigated using a Fourier-transform microwave spectrometer in a supersonic expansion. Torsional splittings arising from two inequivalent methyl internal rotors in combination with hyperfine splittings due to the nuclear quadrupole coupling of the 14N nucleus were observed. The experiments were accompanied by quantum chemical calculations. A total of 1561 rotational lines were assigned and fitted in global fits using the programs XIAM and BELGI-Cs-2Tops-hyperfine, both achieved the measurement accuracy of 4kHz. Local separate fits were also performed to verify the correctness of the assignment. Accurate experimental molecular and internal rotation parameters could be deduced and compared to the calculated ones. The barrier to internal rotation of the 2-methyl rotor was determined to be 277.830(26) cm-1, essentially the same as the value of about 280cm-1 found for 2-methylpyrrole but lower than the value of 317cm-1 found for 2,5-dimethylpyrrole. The torsional barrier value of the 4-methyl rotor is 262.210(27) cm-1, slightly higher than the value of 246cm-1 found for 3-methylpyrrole. Benchmarking the rotational constants for 2,4- and 2,5-dimethylpyrrole revealed that the MP2/6-31G(d,p) level could be helpful to guide the assignment of microwave spectra of pyrrole derivatives.