The many-body expansion approach to ab initio calculation of electric field gradients in molecular crystals.

Accurate calculation of electric field gradients (EFGs) in molecular crystals, despite big advances in ab initio techniques, is still a challenge. Here, we present a new approach to calculate the EFGs in molecular crystals by employing the many-body expansion (MBE) technique with electrostatic embedding. This allows for (i) a reduction in the computational cost or an alternative increase in the level of theory (we use the MP2/6-311++G) and (ii) the ability to monitor EFG convergence by progressively adding more surrounding molecules and/or adding higher many-body interactions.

N NQR spectroscopy reveals the proton position in N-HN bonds: a case study with proton sponges.

The position of protons in hydrogen bonds is often uncertain to some degree, as the technique most often used for structure determination, X-ray diffraction, is sensitive to electron density, which is not particularly abundant around protons. In hydrogen bonds, protons introduce an additional problem: the potential for proton motion is inherently anharmonic and thus requires the consideration of nuclear quantum effects (NQEs). Here, we demonstrate that 14N NQR spectroscopy is able to rather accurately determine proton positions in N-HN bonds, in certain cases with an accuracy comparable to that of X-ray and neutron diffraction at room temperature.

N NQR lineshape in nanocrystals: An ab initio investigation of urea.

N nuclear quadrupole resonance (NQR) lineshapes mostly contain information of low interest, although in nanocrystals they may display some unexpected behaviour. In this work, we present an ab initio computational study of the N NQR lineshapes in urea nanocrystals as a function of the nanocrystal size and geometry, focusing on the surface induced broadening of the lineshapes. The lineshapes were obtained through a calculation of the electric field gradient for each nitrogen site in the nanocrystal separately, taking into account the individual crystal field by embedding the molecule of interest in a suitable lattice of point multipoles representing other urea molecules in the nanocrystal.

(1)H-(14)N cross-relaxation spectrum analysis in sildenafil and sildenafil citrate.

Here we describe a method for the extraction of (14)N quadrupole parameters from a (1)H-(14)N cross-relaxation spectrum by fitting the lineshapes of the (14)N quadrupole transitions. The procedures used typically to fit quadrupole lineshapes are not directly applicable to fit the (1)H-(14)N cross-relaxation spectrum, because the presence of proton homonuclear dipolar interaction broadens the lineshapes considerably and prevents a reliable determination of Cq and η from a single lineshape. Instead, one must fit two or even three lineshapes originating from the same nitrogen site simultaneously.

Polymorphism and disorder in natural active ingredients. Low and high-temperature phases of anhydrous caffeine: Spectroscopic ((1)H-(14)N NMR-NQR/(14)N NQR) and solid-state computational modelling (DFT/QTAIM/RDS) study.

The polymorphism of anhydrous caffeine (1,3,7-trimethylxanthine; 1,3,7-trimethyl-1H-purine-2,6-(3H,7H)-dione) has been studied by (1)H-(14)N NMR-NQR (Nuclear Magnetic Resonance-Nuclear Quadrupole Resonance) double resonance and pure (14)N NQR (Nuclear Quadrupole Resonance) followed by computational modelling (Density Functional Theory, supplemented Quantum Theory of Atoms in Molecules with Reduced Density Gradient) in solid state. For two stable (phase II, form β) and metastable (phase I, form α) polymorphs the complete NQR spectra consisting of 12 lines were recorded. The assignment of signals detected in experiment to particular nitrogen sites was verified with the help of DFT.

Quantitative Analysis of Hydration Using Nitrogen-14 Nuclear Quadrupole Resonance.

Hydration is a quite common process in pharmaceutical solids. Sometimes it is desirable, as it stabilizes the crystal structure; in other cases it is unwanted, as it changes the physical and chemical properties of drugs. We here use (14)N NQR spectroscopy to quantitatively analyze hydration of a model compound, 5-aminotetrazole.

WURST-QCPMG sequence and "spin-lock" in ¹⁴N nuclear quadrupole resonance.

¹⁴N nuclear quadrupole resonance (NQR) is a promising method for the analysis of pharmaceuticals or for the detection of nitrogen based illicit compounds, but so far, the technique is still not widely used, mostly due to the very low sensitivity. This problem is already acute in the preliminary NQR stage, when a compound is being examined for the first time and the NQR frequencies are being searched for, by scanning a wide frequency range step-by-step. In the present work, we experimentally show how to increase the efficiency of this initial stage by using a combination of a wideband excitation achieved with frequency swept pulses (WURST) and a "spin-lock" state obtained with a quadrupolar-CPMG (QCPMG) sequence.

Capacitor-based detection of nuclear magnetization: nuclear quadrupole resonance of surfaces.

We demonstrate excitation and detection of nuclear magnetization in a nuclear quadrupole resonance (NQR) experiment with a parallel plate capacitor, where the sample is located between the two capacitor plates and not in a coil as usually. While the sensitivity of this capacitor-based detection is found lower compared to an optimal coil-based detection of the same amount of sample, it becomes comparable in the case of very thin samples and even advantageous in the proximity of conducting bodies. This capacitor-based setup may find its application in acquisition of NQR signals from the surface layers on conducting bodies or in a portable tightly integrated nuclear magnetic resonance sensor.

Aplicability of TNT "super-Q detection" to multipulse sequences.

The use of high-Q probes to increase the sensitivity in NMR and NQR is a well-known technique, however very high Q values are associated with several limitations. This paper explores the (14)N NQR multipulse detection of trinitrotoluene (TNT) signal-to-noise ratio as a function of the pickup coil Q factor, with a particular emphasis on the "super-Q" regime, where probe bandwidth becomes narrower than the NQR linewidths. We have used a mixed experimental-theoretical approach to find the TNT Q-dependent signal-to-noise value which avoided the inconvenient construction of a probe at every Q.

Improving 14N nuclear quadrupole resonance detection of trinitrotoluene using off-resonance effects.

The off-resonance dependence of the amplitudes of the six dominant (14)N nuclear quadrupole resonance (NQR) lines in commercial polymorphic trinitrotoluene (TNT) sample were experimentally determined for a wide range of experimental parameters when irradiated with the spin-lock spin-echo (SLSE) pulse sequence. We find that the amplitudes off-resonance dependence follows a sinc-like function with an additional modulation due to the spacing between the RF pulses. This dependence can be very well modeled with expressions we have derived for a single site (14)N NQR in paranitrotoluene (PNT).

TNT detection with 14N NQR: multipulse sequences and matched filter.

Nuclear quadrupole resonance (NQR) has a distinct potential to verify the presence of nitrogen bearing substances based on the unequivocal signatures of their spectra. Therefore, this technique is especially suitable for remote detection of illicit substances and explosives. Unfortunately, the inherent signal-to-noise of the most abundant explosive trinitrotoluene (TNT) is very low.

Relaxation during spin-lock spin-echo pulse sequence in (14)N nuclear quadrupole resonance.

In this work, we investigate off-resonance effect on the (14)N nuclear quadrupole resonance magnetization decay during the spin-lock spin-echo pulse sequence (SLSE). The compound chosen for this study is paranitrotoluene with a single (14)N site, which represents a suitable simplified model for the explosive trinitrotoluene with six nonequivalent (14)N sites. We find that the quasi-steady state magnetization exhibits dips at particular frequency offsets and more interestingly that its decay rate T(2 eff) (-1) exhibits similar dips (slower decay) at the same frequency offsets.

17O and 29Si NMR parameters of MgSiO3 phases from high-resolution solid-state NMR spectroscopy and first-principles calculations.

The 29Si and 17O NMR parameters of six polymorphs of MgSiO3 were determined through a combination of high-resolution solid-state NMR and first-principles gauge including projector augmented wave (GIPAW) formalism calculations using periodic boundary conditions. MgSiO3 is an important component of the Earth's mantle that undergoes structural changes as a function of pressure and temperature. For the lower pressure polymorphs (ortho-, clino-, and protoenstatite), all oxygen species in the 17O high-resolution triple-quantum magic angle spinning (MAS) NMR spectra were resolved and assigned.