A Computational Study on Closed-Shell Molecular Hexafluorides MF6 (M=S, Se, Te, Po, Xe, Rn, Cr, Mo, W, U) - Molecular Structure, Anharmonic Frequency Calculations, and Prediction of the NdF6 Molecule.

Quantum chemical methods were used to study the molecular structure and anharmonic IR spectra of the experimentally known closed-shell molecular hexafluorides MF6 (M=S, Se, Te, Xe, Mo, W, U). First, the molecular structures and harmonic frequencies were investigated using Density Functional Theory (DFT) with all-electron basis sets and explicitly considering the influence of spin-orbit coupling. Second, anharmonic frequencies and IR intensities were calculated with the CCSD(T) coupled cluster method and compared, where available, with IR spectra recorded by us. These comparisons showed satisfactory results. The anharmonic IR spectra provide means for identifying experimentally too little studied or unknown MF6 molecules with M=Cr, Po, Rn. To the best of our knowledge, we predict the NdF6 molecule for the first time and show it to be a true local minimum on the potential energy surface. We used intrinsic bond orbital (IBO) analyses to characterize the bonding situation in comparison with the UF6 molecule.

Molecular Structure, Vibrational Spectrum and Conformational Properties of 4-(4-Tritylphenoxy)phthalonitrile-Precursor for Synthesis of Phthalocyanines with Bulky Substituent.

By DFT method with B3LYP, PBE, CAM-B3LYP, and B97D functionals, it was found that the molecule 4-(4-tritylphenoxy)phthalonitrile (TPPN) has four conformers. The geometric structure, vibrational frequencies, electronic characteristics, and thermodynamic functions of conformers, as well as the structure and energy of transition states, were determined. IR spectrum of TPPN film contains vibrational bands belonging to different conformers. The assignment of bands was performed basing the distribution of normal vibration energy on internal coordinates. A synchronous electron diffraction/mass spectrometric experiment was performed to determine the structure of conformers in a saturated TPPN vapor. The elemental composition of the ions recorded in the mass spectrum indicates the thermal stability of TPPN at least up to T = 200 °C. The difference in the structure of tetrasubstituted metal phthalocyanines, which can be synthesized from different TPPN conformers, has been shown.

Synthesis, crystal structure and properties of poly[(µ-2-methyl-pyridine N-oxide-κ2O:O)bis-(µ-thio-cyanato-κ2N:S)cobalt(II)].

The title compound, [Co(NCS)2(C6H7NO)]n or Co(NCS)2(2-methyl-pyridine N-oxide), was prepared by the reaction of Co(NCS)2 and 2-methyl-pyridine N-oxide in methanol. All crystals obtained by this procedure show reticular pseudo-merohedric twinning, but after recrystallization, one crystal was found that had a minor component with only a very few overlapping reflections. The asymmetric unit consists of one CoII cation, two thio-cyanate anions and one 2-methyl-pyridine N-oxide coligand in general positions. The CoII cations are octa-hedrally coordinated by two O-bonding 2-methyl-pyridine N-oxide ligands, as well as two S- and two N-bonding thio-cyanate anions, and are connected via µ-1,3(N,S)-bridging thio-cyanate anions into chains that are linked by µ-1,1(O,O) bridging coligands into layers. No pronounced directional inter-molecular inter-actions are observed between the layers. The 2-methyl-pyridine coligand is disordered over two orientations and was refined using a split model with restraints. Powder X-ray diffraction (PXRD) indicates that a pure sample was obtained and IR spectroscopy confirms that bridging thio-cyanate anions are present. Thermogravimetry and differential thermoanalysis (TG-DTA) shows one poorly resolved mass loss in the TG curve that is accompanied by an exothermic and an endothermic signal in the DTA curve, which indicate the decomposition of the 2-methyl-pyridine N-oxide coligands.

Water rotational relaxation time measurement by shortwave infrared micro spectroscopy(SWIR) at sub-zero temperatures.

The shortwave infrared spectroscopy (SWIR) is the noble method which allows to evaluate the rotational relaxation time of water (RRTW) in a sample. Because SWIR requires the reference sample of pure water, the measurement temperature is limited only at above 0 °C. In this study, we expanded this temperature limitation of SWIR by using alternative reference solutions with freezing points below 0 °C, including sugar and glycerol solutions. The results showed that some reference sample solutions are useable for evaluating RRTW in samples below 0 °C. It was found that RRTW in solution measured by newly proposed SWIR agrees with RRTW measured by dielectric spectroscopy in 10% accuracy when it is shorter than 100psec.

Influence of Partially Carboxylated Powdered Lignocellulose from Oat Straw on Technological and Strength Properties of Water-Swelling Rubber.

The work is aimed at the development of an energy-saving technique involving the partial carboxylation of powdered lignocellulose products from the straw of annual agricultural plants and the use of the obtained products in rubber compositions as a water-swelling filler. Lignocellulose powder from oat straw (composition: α-cellulose-77.0%, lignin-3.8%, resins and fats-1.8%) was used for carboxylation without preliminary separation into components. Microwave radiation was used to activate the carboxylation process. This reduced the reaction time by 2-3 times. The synthesized products were analyzed by IR spectroscopy, thermogravimetry and scanning electron microscopy. Industrial product sodium carboxymethylcellulose (Na-CMC) was used as a swelling filler for comparison. The swelling fillers were fractionated by the sieve method; particles with the size of 0-1 mm were used for filling rubber compounds. The amount of swelling filler was 150 parts per 100 parts of rubber (phr). Due to the high filling of rubber compounds, plasticizer Oxal T-92 was added to the composition of a number of samples to facilitate the processing and uniform distribution of ingredients. The rubber composition was prepared in two stages. In the first stage, ingredients without swelling filler were mixed with rubber on a laboratory two-roll mill to create a base rubber compound (BRC). In the second stage, the BRC was mixed with the swelling filler in a closed laboratory plasti-corder rubber mixer, the Brabender Plasti-Corder® Lab-Station. Vulcanization was carried out at 160 °C. For the obtained samples, the physical-mechanical and sorption properties were determined. It has been shown that the carboxylated powdered lignocellulose from oat straw increases the strength properties of rubber in comparison with Na-CMC. It has been shown that when the carboxylated powdered lignocellulose from oat straw is introduced into the rubber composition, the degree of rubber swelling in aqueous solutions of various mineralizations increases by 50 and 100% in comparison with a noncarboxylated lignocellulose.

Synthesis, crystal structure and properties of tetra-kis-(pyridine-3-carbo-nitrile)-dithio-cyanatoiron(II) and of diaqua-bis-(pyridine-3-carbo-nitrile)-di-thio-cyanatoiron(II) pyridine-3-carbo-nitrile monosolvate.

The reaction of iron thio-cyanate with 3-cyano-pyridine (C6H4N2) leads to the formation of two compounds with the composition [Fe(NCS)2(C6H4N2)4] (1) and [Fe(NCS)2(C6H4N2)2(H2O)2]·2C6H4N2 (2). The asymmetric unit of 1 consists of one iron cation, two thio-cyanate anions and four 3-cyano-pyridine ligands in general positions. The iron cation is octa-hedrally coordinated by two N-bonded thio-cyanate anions and four 3-cyano-pyridine ligands. The complexes are arranged in columns along the crystallographic c-axis direction and are linked by weak C-H⋯N inter-actions. In 2, the asymmetric unit consists of one iron cation on a center of inversion as well as one thio-cyanate anion, one 3-cyano-pyridine ligand, one water ligand and one 3-cyano-pyridine solvate mol-ecule in general positions. The iron cation is octa-hedrally coordinated by two N-bonded thio-cyanate anions, two cyano-pyridine ligands and two water ligands. O-H⋯N and C-H⋯S hydrogen bonding is observed between the water ligands and the solvent 3-cyano-pyridine mol-ecules. In the crystal structure, alternating layers of the iron complexes and the solvated 3-cyano-pyridine mol-ecules are observed. Powder X-ray (PXRD) investigations reveal that both compounds were obtained as pure phases and from IR spectroscopic measurements conclusions on the coordination mode of the thio-canate anions and the cyano-group were made. Thermogravimetric (TG) and differential thermoanalysis (DTA) of 1 indicate the formation of a compound with the composition {[Fe(NCS)2]3(C6H4N2)4}n that is isotypic to the corresponding Cd compound already reported in the literature. TG/DTA of 2 show several mass losses. The first mass loss corresponds to the removal of the two water ligands leading to the formation of 1, which transforms into {[Fe(NCS)2]3(C6H4N2)4}n, upon further heating.

Quality analysis and geographical origin identification of Rosa roxburghii Tratt from three regions based on Fourier transform infrared spectroscopy.

The study aimed to provide new information of Rosa roxburghii Tratt (RRT) for the production of functional foods and distinguish the geographical origins of RRT. The nutritional components of RRT from three regions in China, such as vitamin C, polysaccharides, total flavonoids, and total phenolics, and their antioxidant activities were analyzed by one-way ANOVA. The results of Fourier transform infrared spectroscopy (FT-IR) combined with principal component analysis (PCA), stepwise linear discriminant analysis (SLDA), k-nearest neighbor (k-NN), and support vector machine (SVM) were used to establish discriminant models to identify the geographical origin of RRT. The results of one-way ANOVA showed that the contents of some nutrients and antioxidant activity were significantly different among RRT from different regions and their FT-IR spectra also showed significant differences. The characteristic fingerprint bands of FT-IR (1679-1618 cm-1and 1520-900 cm-1) closely related to the geographical origins of RRT were screened out. Based on SLDA, a discriminant model was established to realize the classification and identification of RRT from different regions and the correct discrimination rate of the testing sample set obtained with the established model reached 100 %. Geographical factors caused the obvious differences in nutritional components and antioxidant activity in RRT. The characteristic fingerprint bands of RRT obtained with FT-IR could be used to identify the geographical origins of RRT more quickly and accurately.

Effect of Magnesium Substitution on Structural Features and Properties of Hydroxyapatite.

Hydroxyapatite (HAP) is the main mineral component of bones and teeth. It is widely used in medicine as a bone filler and coating for implants to promote new bone growth. Ion substitutions into the HAP structure highly affect its properties. One of the most important substituents is magnesium. This paper presents new results obtained using high-precision hybrid density functional theory calculations for Mg/Ca substitutions in HAP in a wide magnesium concentration range within a 2 × 2 × 2 supercell model. Experimental data on the mechanochemical synthesis of HAP-Mg samples with different Mg concentrations are also presented. A comparison between the experiment and the theory showed good agreement: the HAP-Mg unit cell parameters and volume decreased with increasing degree of Mg/Ca substitution. The changes in the distances between the Ca and O, Ca and H, and Mg and O ions upon Mg/Ca substitution in different calcium positions was analyzed. The resulting asymmetry and distortion of the cell parameters were evaluated. It was shown that bulk modulus, energy levels, and band gap depend on the degree of Mg substitutions in the Ca1 and Ca2 positions. The formation energies of Mg/Ca substitutions showed non-monotonic behavior that was different for Ca1 and Ca2 positions. The Ca2 position had a slightly higher probability (~5 meV/f.u.) of substitution than Ca1 position at a Mg concentration x = 0.5. At x = 1, substitution in both positions can coexist. The simulated IR spectra for different Mg/Ca substitutions showed that Mg in the Ca2 position changes the IR spectrum more significantly than Mg in the Ca1 position. Similar changes were recorded in the IR spectra of the synthesized samples. The electronic structure is shown to be sensitive to the number and position of substitutions, which may be used to tweak the optical properties of the HAP-Mg material.

Tests of Dental Properties of Composite Materials Containing Nanohybrid Filler.

Complex composite materials are used in many areas of dentistry. Initially, chemically hardened materials were also used, and in this group nanohybrid composites are highly valued. They are often used today, mainly for the direct reconstruction of damaged hard tooth tissue materials for rebuilding damaged tissues using indirect adhesive techniques. The research was conducted to determine the mechanical properties of materials with nanofillers. The article focuses on methods of important test methods for dental prosthetics: resilience, abrasion, wear test, impact strength, hardness, SEM, and chemical analysis. As part of this work, five different series of hybrid composites with nano-fillers were tested. The mechanical properties of composites, such as compressive strength, microhardness, flexural strength, and modulus of elasticity, depend mainly on the type, particle size, and amount of filler introduced. The obtained test results showed that the type and amount of nanofiller have a significant influence on the mechanical and tribological properties. The introduction of nanofillers allowed us to obtain higher mechanical properties compared to classic materials discussed by other researchers. The study observed a change in vibrations in the IR spectrum, which allowed a comparison of the organic structures of the studied preparations.

Evaluation of the infrared frying on the physicochemical properties of fried apple slices and the deterioration of oil.

The influence of infrared frying (IF) on the physicochemical properties of fried apple slices and the oil deterioration was investigated, considering conventional frying (CF) as a reference. IF had a more favorable impact on the heating rate and thermal efficiency, which subsequently resulted an accelerated moisture removal rate. The oil uptake in infrared-fried apple slices were reduced by 12.9%-17.3%, when compared to the CF, as attributed to the denser and smoother morphological microstructure. The color of apple slices was better preserved in IF and the total phenolic and flavonoid contents had a higher retention rate with the optimal infrared power (2000 W in this study). Additionally, infrared frying was proved to be a promising technology to slow down the oil deterioration rate as was observed from lower values of acid value, and carbonyl value, which was also supported by the results of gas chromatography, FT-IR, and LF-NMR analysis.

Temperature dependence of IR exciton emission spectra in Müller cell intermediate filaments.

Temperature dependences of IR exciton properties in Müller cell (MC) intermediate filaments (IFs) isolated from porcine retina were studied. It was found that the widths of the spectral emission bands in the 2500 cm-1 and 5000 cm-1 energy ranges grow with temperature. It was found that temperature effects on the bandwidth may be described by thermal activation of the low-frequency vibrational modes of the IFs. The average activation energies for the two IR bands were estimated. Considering the dynamics of IR emission, its buildup time was independent on the sample temperature, while its decay time decreased with temperature. Thus, the emission decay rate increased exponentially with the sample temperature. The mechanisms explaining the observed temperature effects were proposed and discussed. Taking into account that MC IFs are capable of transmitting ATP hydrolysis energy within and between cells, with these properties being apparently common for all IFs, these IFs may be used by cells for physical energy transport and communications. As presently reported, temperature effects upon IR exciton spectra should not affect these proposed physiological functions to any significant extent. Therefore, the currently reported data are important for improving our understanding of the physical communication mechanisms operating within and between cells.

Effect of Internal Donors on Raman and IR Spectroscopic Fingerprints of MgCl2/TiCl4 Nanoclusters Determined by Machine Learning and DFT.

To go deep into the origin of MgCl2 supported Ziegler-Natta catalysis we need to fully understand the structure and properties of precatalytic nanoclusters MgCl2/TiCl4 in presence of Lewis bases as internal donors (ID). In this work MgCl2/TiCl4 nanoplatelets derived by machine learning and DFT calculations have been used to model the interaction with ethyl-benzoate EB as ID, with available exposed sites of binary TixCly/MgCl2 systems. The influence of vicinal Ti2Cl8 and coadsorbed TiCl4 on energetic, structural and spectroscopic behaviour of EB has been considered. The adsorption of homogeneous-like TiCl4EB and TiCl4(EB)2 at the various surface sites have been also simulated. B3LYP-D2 and M06 functionals combined with TZVP quality basis set have been adopted for calculations. The adducts have been characterized by computing IR and Raman spectra that have been found to provide specific fingerprints useful to identify surface species; IR spectra have been successfully compared to available experimental data.

Nature of the observed ν(NO) band shift and splitting during the 3D to 2D structural change in transition metal nitroprussides.

The electronic structure and related optical properties of the nitroprusside ion, [Fe(CN)5NO]2-, are dominated by the nitrosyl (NO+) group. The light-induced 2b2(xy) â†’ 7e(π*NO) (Fe â†’ NO) and related appearance of meta-stable isomers for the NO group supports many of the functional properties of metal nitroprussides. In recent studies on the preparation of 2D transition metal nitroprussides from their 3D analogs, we have observed that such a structural change is concomitant with a decrease for the ν(NO) frequency and certain band splitting (unfolding). The 3D to 2D structural modification leads to an increase in the electron density at the iron atom. This results in an enhancement for the π*-back donation, which increases the electron population at the π*2px and π*2py orbitals. These last orbitals are doubly degenerated, and the increase for the π*-back bonding induces the removal of that degeneration via the Jahn-Teller effect. This intuitive mechanism explains the mentioned band unfolding related to the structural change. Such explanation was herein supported by a model based on the normal modes for the FeNO fragment derived from the small oscillation formalism around the equilibrium positions for the involved atoms. This model shows that there is a very close relationship between the deformation of the nitrosyl group (NO+) and the splitting of the IR bands. That is, the less linear the nitrosyl group, the greater the shift and splitting of the mentioned IR band. An excellent coincidence between the frequency values calculated using the model and the experimental ones was observed. The largest difference between the theoretically calculated ν(NO) frequencies and the experimental ones was only 6 cm-1 and 5 cm-1 in representative samples of 2D and 3D transition metal nitroprussides, respectively. The understanding of such an effect could be relevant for the functional properties of these 2D coordination polymers.

The gelation properties of myofibrillar proteins prepared with malondialdehyde and (-)-epigallocatechin-3-gallate.

Impact of malondialdehyde (MDA) and (-)-Epigallocatechin-3-gallate (EGCG) on gelling properties of myofibrillar proteins (MPs) was investigated. Addition of 6 mM MDA enhanced molecular interactions of proteins, thus the strength and elastic modulus (G') of gel were improved. EGCG addition aggravated gel quality deterioration due to further modification of MPs induced by EGCG. Addition of 12 mM MDA jeopardized gel quality according to the increasing of strength and G', but the decreasing of water-holding capacity (WHC), and the collapse of microstructure. Nevertheless, EGCG reacted with MDA forming EGCG-MDA adducts, hence improved gel quality, which was supported by the decreasing of strength, but the increasing of WHC, and the repaired microstructure of gel at 12 mM MDA. Addition of 24 mM MDA severely jeopardized gel quality, which became even worse due to EGCG addition. This work is helpful to understand the impact of MDA and polyphenols on the gel-forming capacity of MPs.

Vibrational Spectra and Molecular Vibrational Behaviors of All-Carboatomic Rings, cyclo[18]carbon and Its Analogues.

The vibrational spectra of cyclo[18]carbon and its analogues, cyclo[2n]carbon (n=3 to 15), were carefully simulated and characterized. The in-plane C-C stretching vibrations shows strong rigidity, while out-of-plane motions seem to be extremely flexible. The solvation effect can enhance signal strengths of the vibrational spectra, but does not evidently change the shape of the spectral curves. The infrared and Raman spectra of cyclo[2n]carbons are quite sensitive to ring size in the range of n=3 to 7, while the size only modestly affects peak positions and strengths for larger rings. Molecular dynamic trajectories show that the fluctuation period of the skeleton of cyclo[18]carbon is basically constant at different temperatures, and they are all about 300 fs. With increase of simulation temperature, the ring distortion due to thermal motion is notable and becomes much stronger. However, neither ring breaking nor isomerization in cyclo[18]carbon is observed during the simulations untill 298.15 K.

Burmese Amber Compared Using Micro-Attenuated Total Reflection Infrared Spectroscopy and Ultraviolet Imaging.

Attenuated Total Reflection (ATR) spectroscopy coupled with a microscope allows for the analysis of specimens without any preparation, spatially correlated with the morphology of the specimen. These characteristics make micro-ATR systems very useful for studying gemstones and in particular amber samples. Indeed, in this report, the micro-ATR technique was used to characterize three Burmite samples, as case studies. Particularly, focusing the ATR crystal spot on the amber surface where a difference in the Ultraviolet (UV) reaction was previously detected, thereby relative differences in the IR spectrum could be analyzed. Here we present a methodology combining the UV imaging technique with the micro-Attenuated total reflection Fourier transform infrared spectroscopy (micro-ATR/FT-IR) analyses, in order to correlate the fluorescence information with the molecular vibrational modes of amber and their relative spatial distribution. Finally, this work is intended as an initial methodology study and part of the amber characterization project, focused on characterizing the Burmese amber collection of the Peretti Museum Foundation from several disciplines (i.e., palaeoentomology, vibrational spectroscopy, neutron tomography, etc.).

Data on spectra of lanthanide-containing polyoxometalate.

Lanthanide-containing polyoxometalate (POM) is one of the presently most active groups as the properties of POM can be modified by incorporated transition metal ions. There are several reported transition metal ion contained POMs such as one Ln ion-POM with Keggin POM frameworks and a novel sandwich"-type, which consists of two open Wells-Dawson anions and three Ln ions [1-3]. In this data article, UV-vis spectra and FTIR spectra as well as the elemental analysis are shown for prepared ß-K7H8[Er3O3(SiW9O34)2]·25H2O and ß-K12H5[Sm3O3(SiW9O34)2]·18H2O, these results are intended to provide support for lanthanide-containing POM due to the lack of information on lanthanide-containing POM. The UV-vis spectra and FTIR spectra as well as the elemental analysis are shown for prepared ß-K7H8[Er3O3(SiW9O34)2]·25H2O and ß-K12H5[Sm3O3(SiW9O34)2]·18H2O were not reported in the article [4] are given. The data is related to the research article "Enhancing Electrofluorochromic Efficiency through  C 30 H 31 N 6 + -Sensitized Layer-by-layer Polyoxometalate Films" [4].

Understanding the interfacial interactions of bioinspired chitosan-calcite nanocomposites by first principles molecular dynamics simulations and experimental FT-IR spectroscopy.

The interfacial structures and bonding mechanism of the adsorption of chitosan monomers (GlcN and GlcNAc) on calcite (104) surface are investigated using first principles molecular dynamics simulations. It is revealed that the strong coordination CaO bonds are formed between five-fold coordinated Ca atoms on calcite surface and O atoms of hydroxyl groups (OH) and acetyl groups of chitosan in the chitosan-calcite nanocomposites, improving the chemical compatibility between organic and inorganic phases at the interface in the natural occurring nacre. Although, the presence of interfacial hydrogen bonds is also confirmed by analyzing the valence electron density difference in terms of induced dipole, the evolution of the equilibrium adsorption geometry is found to be mainly governed interfacial CaO coordination bonds. The amide group (NH2) of chitosan binds with calcite at the interface mainly through the formation of weak hydrogen bond. The predicted interfacial electronic structure can be either conductive (GlcNAc) or insulating (GlcN). The frequencies of the characteristic peaks in the calculated total and partial vibrational densities of states of GlcN/calcite systems are found to be in agreement with the FT-IR spectrum of the experimentally prepared chitosan-calcite nanocomposites, crucially validating the modelling structures and computational methodology employed in current work. Theoretical results strongly indicate that the peculiar adsorption in FT-IR spectrum at 2500 cm-1 is related to the presence of free GlcN molecule due to the hydrolysis of chitosan in aqueous solution.

Analysis of intraspecific seed diversity in Astragalus aquilanus (Fabaceae), an endemic species of Central Apennine.

This work aims to study seeds of the endemic species Astragalus aquilanus from four different populations of central Italy. We investigated seed morpho-colorimetric features (shape and size) and chemical differences (through infrared spectroscopy) among populations and between dark and light seeds. Seed morpho-colorimetric quantitative variables, describing shape, size and colour traits, were measured using image analysis techniques. Fourier transform infrared (FT-IR) spectroscopy was used to attempt seed chemical characterisation. The measured data were analysed by step-wise linear discriminant analysis (LDA). Moreover, we analysed the correlation between the four most important traits and six climatic variables extracted from WorldClim 2.0. The LDA on seeds traits shows clear differentiation of the four populations, which can be attributed to different chemical composition, as confirmed by Wilk's lambda test (P < 0.001). A strong correlation between morphometric traits and temperature (annual mean temperature, mean temperature of the warmest and coolest quarter), colorimetric traits and precipitation (annual precipitation, precipitation of wettest and driest quarter) was observed. The characterisation of A. aquilanus seeds shows large intraspecific plasticity both in morpho-colorimetric and chemical composition. These results confirm the strong relationship between the type of seed produced and the climatic variables.

Impact of Sodium Cationization on Gas-Phase Conformations of DNA and RNA Cytidine Mononucleotides.

Gas-phase conformations of the sodium-cationized forms of the 2'-deoxycytidine and cytidine mononucleotides, [pdCyd+Na]+ and [pCyd+Na]+, are examined by infrared multiple photon dissociation action spectroscopy. Complimentary electronic structure calculations at the B3LYP/6-311+G(2d,2p)//B3LYP/6-311+G(d,p) level of theory provide candidate conformations and their respective predicted IR spectra for comparison across the IR fingerprint and hydrogen-stretching regions. Comparisons of the predicted IR spectra and the measured infrared multiple photon dissociation action spectra provide insight into the impact of sodium cationization on intrinsic mononucleotide structure. Further, comparison of present results with those reported for the sodium-cationized cytidine nucleoside analogues elucidates the impact of the phosphate moiety on gas-phase structure. Across the neutral, protonated, and sodium-cationized cytidine mononucleotides, a preference for stabilization of the phosphate moiety and nucleobase orientation is observed, although the details of this stabilization differ with the state of cationization. Several low-energy conformations of [pdCyd+Na]+ and [pCyd+Na]+ involving several different orientations of the phosphate moiety and sugar puckering modes are observed experimentally.