Spin–spin coupling constants in linear substituted HCN clusters

The indirect nuclear spin–spin coupling constants of homogeneous hydrogen-bonded HCN clusters are compared with those of inhomogeneous HCN clusters where one of the terminal HCN molecules is substituted by its isomer HNC and by LiCN. Both the intra- and intermolecular (across the hydrogen bond) coupling constants are calculated for the linear form of the clusters containing up to three molecular monomers using different hybrid DFT functionals. The geometry of the monomers and clusters is optimised at the B3LYP/6-311++G(d,p) level. The effect of substitution by the ionic compound LiCN on the coupling constants of HCN is found to be more pronounced than that by HNC. The Ramsey parameters that form the total spin–spin coupling constants are also analysed individually. Among the four Ramsey parameters, the Fermi Contact term is found to be the dominant contributor to the total coupling constants in most cases. The presence of LiCN in the cluster tends to decrease the intramolecular Fermi Contact values, while HNC increases the same in all dimers and trimers. The contributions of localised molecular orbitals have been analysed for the HCN–HNC cluster to obtain some additional insight about the SSCC transmission mechanism along the coupling pathway.     

Two-, three-, and four-bond N–F spin–spin coupling constants in fluoroazines

Ab initio EOM-CCSD calculations have been performed to investigate 2-, 3- and 4-bond ¹⁵N–¹⁹F coupling constants in mono-, di-, and trifluoroazines. ²J(N–F) values are negative and are dominated by the Fermi-contact (FC) term. Absolute values of ²J(N–F) tend to decrease as the number of N atoms in the ring increases, and may also be influenced by the number and positions of C–F bonds. ³J(N–F) values are positive with three exceptions, are usually dominated by the FC term, and also tend to decrease as the number of N atoms increases. The three molecules which have negative values of ³J(N–F) have dominant negative paramagnetic-spin orbit (PSO) terms, and are structurally similar insofar as they have an intervening C–F bond between the N and the coupled F. ⁴J(N–F) values are negative because the PSO, FC, and spin-dipole (SD) terms are negative, with only one exception. Four molecules have significantly greater values of ⁴J(N–F). These are structurally similar with the coupled N bonded to two other N atoms. The computed EOM-CCSD ⁿJ(N–F) coupling constants are in good agreement with the few experimental values that are available.     

Molecular properties in the Tamm–Dancoff approximation: indirect nuclear spin–spin coupling constants

The Tamm–Dancoff approximation (TDA) can be applied to the computation of excitation energies using time-dependent Hartree–Fock (TD-HF) and time-dependent density-functional theory (TD-DFT). In addition to simplifying the resulting response equations, the TDA has been shown to significantly improve the calculation of triplet excitation energies in these theories, largely overcoming issues associated with triplet instabilities of the underlying reference wave functions. Here, we examine the application of the TDA to the calculation of another response property involving triplet perturbations, namely the indirect nuclear spin–spin coupling constant. Particular attention is paid to the accuracy of the triplet spin–dipole and Fermi-contact components. The application of the TDA in HF calculations leads to vastly improved results. For DFT calculations, the TDA delivers improved stability with respect to geometrical variations but does not deliver higher accuracy close to equilibrium geometries. These observations are rationalised in terms of the ground- and excited-state potential energy surfaces and, in particular, the severity of the triplet instabilities associated with each method. A notable feature of the DFT results within the TDA is their similarity across a wide range of different functionals. The uniformity of the TDA results suggests that some conventional evaluations may exploit error cancellations between approximations in the functional forms and those arising from triplet instabilities. The importance of an accurate treatment of correlation for evaluating spin–spin coupling constants is highlighted by this comparison.     

The NMR indirect nuclear spin–spin coupling constant of the HD molecule

We present new calculated and experimental values of the NMR indirect nuclear spin–spin coupling constant in HD. In the quantum-chemical ab initio calculations, the full configuration-interaction (FCI) method is used, yielding an equilibrium value of 41.22?Hz in the basis-set limit. Adding a calculated zero-point vibrational correction of 1.89?Hz and a temperature correction of 0.20?Hz at 300?K, we obtain a total calculated spin–spin coupling constant of J _FCI(HD)?=?43.31(5)?Hz at 300?K. This result is within the error bars of the experimental gas-phase NMR value, J _exp(HD)?=?43.26(6)?Hz, obtained by extrapolating values measured in HD–He mixtures to zero density.     

Prediction of the 1H NMR spectra of epoxy-fused cyclopentane derivatives by calculations of chemical shifts and spin–spin coupling constants

¹H NMR spectra of epoxy-fused cyclopentane derivatives have been computationally investigated with density functional calculations in order to unravel the shielding effect of the epoxy ring on the ¹H NMR chemical shifts of N-substituted epoxy-fused cyclopentane-3, 5-diol derivatives. Both ¹H NMR chemical shifts and spin–spin coupling constants have been calculated with the WP04/cc-pVTZ level of theory in solution. The WP04/cc-pVTZ// B3LYP/6-31+G(d) methodology has been found to reproduce the best experimental results on epoxy-fused cyclopentane derivatives. This study is expected to lead experimentalists in their endeavour to characterize epoxy-fused cyclic systems with ease.     

Effects of vibrational averaging on coupled cluster calculations of spin–spin coupling constants for hydrocarbons

We present vibrationally corrected nuclear spin–spin coupling constants for four hydrocarbons with different types of carbon–carbon bonds calculated with coupled cluster (CC) theory. First, we perform a systematic basis set investigation on acetylene for all of the four contributions (Fermi-contact, spin-dipole, para- and diamagnetic spin–orbit) to the spin–spin coupling constants and subsequently choose basis sets of sufficient flexibility to describe converged electronic properties. Then, in order to describe the effects of vibrational motion for the studied molecules we perform a Taylor expansion in the normal coordinates up to second order – a method that is well known for both its quality and efficiency – and rigorously estimate the resulting contribution for all types of spin–spin coupling constants. Combined, this allows us to obtain highly accurate benchmark estimates of the spin–spin coupling constants for acetylene, ethylene, ethane, and cyclopropane. This work provides one of the first systematic benchmarks of zero-point vibrational contributions to spin–spin coupling constants in poly-atomic molecules using the reliable CC theory and it is thus an important reference for further research within in-silico spin–spin coupling constant determination. We note that earlier computational estimates of zero-point vibrational effects agree well with those presented here (for acetylene, ethylene, and cyclopropane) while vibrational corrections for ethane are reported for the first time.     

Theory of spin polarization in mesoscopic spin–orbit coupling systems

We establish a general formalism of the bulk spin polarization (BSP) and the current-based spin polarization (CSP) for mesoscopic ferromagnetic and spin–orbit interaction (SOI) semiconducting systems. Based on this formalism, we reveal the basic properties of BSP and CSP and their relationships. The BSP describes the intrinsic spin polarized properties of devices. The CSP depends on both intrinsic parameters of device and the incident current. For the non-spin-polarized incident current with the in-phase spin-phase coherence, CSP equals to BSP. We give analytically the BSP and CSP of several typical nanodevice models, ferromagnetic nanowire, Rashba nanowire and rings. These results provide basic physical behaviors of BSP and CSP and their relationships.     

Density-functional theory calculation of the nuclear magnetic resonance indirect nuclear spin—spin coupling constants in C60

Density-functional theory is used to study the nuclear magnetic resonance (NMR) indirect nuclear spin-spin coupling constants in C₆₀. Knowledge of these coupling constants may help in the analysis of future experimental NMR studies of ¹³C-enriched C₆₀. At the Becke 3-parameter Lee-Yang-Parr (B3LYP) Kohn-Sham level, the one-bond couplings within pentagons and between pentagons are 62 Hz and 77 Hz, respectively; the corresponding geminal couplings are 7 Hz and 1 Hz, respectively. Except for the vicinal couplings (about 4 Hz), the long-range couplings are all 1 Hz or smaller. This is the largest theoretical calculation to date of the complete set of indirect nuclear spin-spin coupling constants of a molecular system; it has been made possible by solving the response equations only for the perturbing operators related to one nuclear magnetic moment, making the calculation feasible.     

Conductance dips and spin precession in a nonuniform waveguide with spin–orbit coupling

An infinite waveguide with a nonuniformity, a segment of finite length with spin–orbit coupling, is considered in the case when the Rashba and Dresselhaus parameters are identical. Analytical expressions have been derived in the single-mode approximation for the conductance of the system for an arbitrary initial spin state. Based on numerical calculations with several size quantization modes, we have detected and described the conductance dips arising when the waves are localized in the nonuniformity due to the formation of an effective potential well in it. We show that allowance for the evanescent modes under carrier spin precession in an effective magnetic field does not lead to a change in the direction of the average spin vector at the output of the system.     

GSI anomaly and spin–rotation coupling

We propose a model in which a recently reported modulation in the decay of the hydrogenlike ions ¹⁴⁰Pr⁵⁸⁺, ¹⁴²Pm⁶⁰⁺ and ¹²²I⁵²⁺ arises from the coupling of rotation to the spin of electron and nucleus. The model shows that the spin–spin coupling of electron and nucleus does not contribute to the modulation and predicts that the anomaly cannot be observed if the motion of the ions is rectilinear, or if the ions are stopped in a target. It also supports the notion that the modulation frequency is proportional to the inverse of the atomic mass and that no modulation is expected for the β⁺${\beta }^{+}$-decay. The model predicts that for He-like ions the modulation is still present.     

Direct spin–phonon coupling of spin-flip relaxation in quantum dots

Within the frame of the Pavlov–Firsov spin–phonon coupling model, we study the spin-flip assisted by the acoustical phonon scattering between the first-excited state and the ground state in quantum dots. We analyze the behaviors of the spin relaxation rates as a function of an external magnetic field and lateral radius of quantum dot. The different trends of the relaxation rates depending on the magnetic field and lateral radius are obtained, which may serve as a channel to distinguish the relaxation processes and thus control the spin state effectively.     

Density-functional calculations of the nuclear magnetic shielding and indirect nuclear spin–spin coupling constants of three isomers of C20

The parameters of the nuclear magnetic resonance (NMR) spectrum – shielding constants and indirect spin–spin coupling constants – of three isomers of C₂₀ are studied using density-functional theory. The performance of different exchange–correlation functionals is analysed by optimising the geometry for the ring, bowl and cage isomers, followed by a computation of the NMR constants at the optimised structure. The results are analysed and rationalised by performing comparisons of the three isomers with one another and with related systems such as polyynes (for the ring), o-benzyne (for the bowl) and C₆₀ (for the cage). The shielding and spin–spin parameters calculated using the Perdew–Burke–Ernzerhof (PBE) exchange–correlation functional are sufficiently reliable to assist in future experimental NMR studies of C₂₀ and, in particular, the identification of its isomers.     

Kink-like breathers in Bose–Einstein condensates with helicoidal spin–orbit coupling

We report a kind of kink-like breathers in one-dimensional Bose–Einstein condensates (BECs) with helicoidal spin–orbit coupling (SOC), on whose two sides the background densities manifest obvious difference (called kink amplitude). The kink amplitude and shape of breather can be adjusted by the strength and period of helicoidal SOC, and its atomic number in two components exchanges periodically with time. The SOC has similar influence on the kink amplitude and the exchanged atomic number, especially when the background wave number is fixed. It indicates that the oscillating intensity of breather can be controlled by adjusting initial kink amplitude. Our work showcases the great potential of realizing novel types of breathers through SOC, and deepens our understanding on the formation mechanisms of breathers in BECs.     

Current-induced nonequilibrium spin polarization in semiconductor-nanowire/s-wave superconductor junctions with strong spin–orbit coupling

We have studied the characteristics of current-induced nonequilibrium spin polarization in semiconductor-nanowire/swave superconductor junctions with strong spin–orbit coupling. It was found that within some parameter regions the magnitude of the current-induced nonequilibrium spin polarization density in such structures will increase(or decrease) with the decrease(or increase) of the charge current density, in contrast to that found in normal spin–orbit coupled semiconductor structures. It was also found that the unusual characteristics of the current-induced nonequilibrium spin polarization in such structures can be well explained by the effect of the Andreev reflection.     

Zeeman coupling in low-carrier antiferromagnetic conductors with strong spin–orbit interaction

I show that, in commensurate Néel antiferromagnetic conductors with inversion symmetry, the substantial momentum dependence of the Zeeman term survives strong spin–orbit coupling and substantial magnetic anisotropy. I illustrate this by a simple example.     

Tunable valley filter efficiency by spin–orbit coupling in silicene nanoconstrictions

Valley filter is a promising device for producing valley polarized current in graphene-like two-dimensional honeycomb lattice materials. The relatively large spin–orbit coupling in silicene contributes to remarkable quantum spin Hall effect, which leads to distinctive valley-dependent transport properties compared with intrinsic graphene. In this paper,quantized conductance and valley polarization in silicene nanoconstrictions are theoretically investigated in quantum spinHall insulator phase. Nearly perfect valley filter effect is found by aligning the gate voltage in the central constriction region. However, the valley polarization plateaus are shifted with the increase of spin–orbit coupling strength, accompanied by smooth variation of polarization reversal. Our findings provide new strategies to control the valley polarization in valleytronic devices.