Microwave spectroscopic and computational analyses of the phenylacetylene⋯methanol complex: insights into intermolecular interactions.

The microwave spectra of five isotopologues of phenylacetylene⋯methanol complex, C6H5CCH⋯CH3OH, C6H5CCH⋯CH3OD, C6H5CCH⋯CD3OD, C6H5CCD⋯CH3OH and C6H5CCH⋯13CH3OH, have been observed through Fourier transform microwave spectroscopy. Rotational spectra unambiguously unveil a specific structural arrangement characterised by dual interactions between the phenylacetylene and methanol. CH3OH serves as a hydrogen bond donor to the acetylenic π-cloud while concurrently accepting a hydrogen bond from the ortho C-H group of the PhAc moiety. The fitted rotational constants align closely with the structural configuration computed at the B3LYP-D3/aug-cc-pVDZ level of theory. The transitions of all isotopologues exhibit doublets owing to the methyl group's internal rotation within the methanol molecule. Comprehensive computational analyses, including natural bond orbital (NBO) analysis, atoms in molecules (AIM) theory, and non-covalent interactions (NCI) index plots, reveal the coexistence of both O-H⋯π and C-H⋯O hydrogen bonds within the complex. Symmetry adapted perturbation theory with density functional theory (SAPT-DFT) calculations performed on the experimentally determined geometry provide an insight into the prominent role of electrostatic interactions in stabilising the overall structural arrangement.

Unified classification of non-covalent bonds formed by main group elements: a bridge to chemical bonding.

Using correlation plots of binding energy and electron density at the bond critical point, we investigated the nature of intermolecular non-covalent bonds (D-X⋯A, where D = O/S/F/Cl/Br/H, mostly, X = main group elements (except noble gases), A = H2O, NH3, H2S, PH3, HCHO, C2H4, HCN, CO, CH3OH, and CH3OCH3). The binding energies were calculated at the MP2 level of theory, followed by Atoms in Molecules (AIM) analysis of the ab initio wave functions to obtain the electron density at the bond critical point (BCP). For each non-covalent bond, the slopes of the binding energy versus electron density plot have been determined. Based on their slopes, non-covalent bonds are classified as non-covalent bond closed-shell (NCB-C) or non-covalent bond shared-shell (NCB-S). Intriguingly, extrapolating the slopes of the NCB-C and NCB-S cases leads to intramolecular "ionic" and "covalent" bonding regimes, establishing a link between such intermolecular non-covalent and intramolecular chemical bonds. With this new classification, hydrogen bonds and other non-covalent bonds formed by a main-group atom in a covalent molecule are classified as NCB-S. Atoms found in ionic molecules generally form NCB-C type bonds, with the exception of carbon which also forms NCB-C type bonds. Molecules with a tetravalent carbon do behave like ions in ionic molecules such as NaCl and interact with other molecules through NCB-C type bonds. As with the chemical bonds, there are some non-covalent bonds that are intermediate cases.

Recent advances in in silico design and characterization of superalkali-based materials and their potential applications: A review.

In the advancement of novel materials, chemistry plays a vital role in developing the realm where we survive. Superalkalis are a group of clusters/molecules having lower ionization potentials (IPs) than that of the cesium atom (3.89 eV) and thus, show excellent reducing properties. However, the chemical industry and material science both heavily rely on such reducing substances; an in silico approach-based design and characterization of superalkalis have been the focus of ongoing studies in this area along with their potential applications. However, although superalkalis have been substantially sophisticated materials over the past couple of decades, there is still room for enumeration of the recent progress going on in various interesting species using computational experiments. In this review, the recent developments in designing/modeling and characterization (theoretically) of a variety of superalkali-based materials have been summarized along with their potential applications. Theoretically acquired properties of some novel superalkali cations (Li3 +) and C6Li6 species, etc. for capturing and storing CO2/N2 molecules have been unveiled in this report. Additionally, this report unravels the first-order polarizability-based nonlinear optical (NLO) response features of numerous computationally designed novel superalkali-based materials, for instance, fullerene-like mixed-superalkali-doped B12N12 and B12P12 nanoclusters with good UV transparency and mixed-valent superalkali-based CaN3Ca (a high-sensitivity alkali-earth-based aromatic multi-state NLO molecular switch, and lead-founded halide perovskites designed by incorporating superalkalis, supersalts, and so on) which can indeed be used as a new kind of electronic nanodevice used in designing hi-tech NLO materials. Understanding the mere interactions of alkalides in the gas and liquid phases and the potential to influence how such systems can be extended and applied in the future are also highlighted in this survey. In addition to offering an overview of this research area, it is expected that this review will also provide new insights into the possibility of expanding both the experimental synthesis and the practical use of superalkalis and their related species. Superalkalis present the intriguing possibility of acting as cutting-edge construction blocks of nanomaterials with highly modifiable features that may be utilized for a wide-ranging prospective application.

Structure and Internal Motions of a Multifunctional Alcohol-Water Complex: Rotational Spectroscopy of the Propargyl Alcohol···H2O Dimer.

We have studied the rotational spectra of the propargyl alcohol (PA)-water complex using a pulsed-nozzle Fourier transform microwave spectrometer. A hydrogen-bonded ring structure is observed. The propargyl alcohol acts as an H-bond donor to form a strong O-H···O bond with H2O, and H2O donates back an H-bond to the acetylenic moiety, forming a weak O-H···π bond. Splittings of the rotational transitions were observed, which are indicative of internal motions of the H2O fragment. The two lowest-energy conformers differ only in the position of the nonbonded hydrogen of H2O. Several isotopic substitutions were carried out to ascertain the position of the nonbonded hydrogen of H2O. Rotational spectroscopy helps to assign the observed structure to one, though it would be vibrationally averaged with a shallow potential along some coordinates, which could interchange the two conformers. These results are compared with earlier results on several alcohol-water complexes to understand the donor-acceptor capabilities of the OH groups in alcohol-water complexes. An empirical correlation between pKa and H-bond donor ability has been observed.

Isolation of a Halogen-Bonded Complex Formed between Methane and Chlorine Monofluoride and Characterisation by Rotational Spectroscopy and Ab Initio Calculations.

A halogen-bonded complex formed between methane and chlorine monofluoride has been isolated in the gas phase before the reaction between the components and has been characterised through its rotational spectrum, which is of the symmetric-top type but only exhibits K = 0 type transitions at the low effective temperature of the pulsed-jet experiment. Spectroscopic constants for two low-lying states that result from internal rotation of the CH4 subunit were detected for each of the two isotopic varieties H4C···35ClF and H4C···37ClF and were analysed to show that ClF lies on the symmetry axis with Cl located closer than F to the C atom, at the distance r0(C···Cl) ≅ 3.28 Å and with an intermolecular stretching force constant kσ ≅ 4 N m-1. Ab initio calculations at the explicitly correlated level CCSD(T)(F12c)/cc-pVTZ-F12 show that in the equilibrium geometry, the ClF molecule lies along a C3 axis of CH4 and Cl is involved in a halogen bond. The Cl atom points at the nucleophilic region identified on the C3 axis, opposite the unique C-H bond and somewhere near the C atom and the tetrahedron face centre, with re(C···Cl) = 3.191 Å. Atoms-in-molecules (AIM) theory shows a bond critical point between Cl and C, confirming the presence of a halogen bond. The energy that is required to dissociate the complex from the equilibrium conformation into its CH4 and ClF components is only De ≅ 5 kJ mol-1. A likely path for the internal rotation of the CH4 subunit is identified by calculations at the same level of theory, which also provide the variation of the energy of the system as a function of the motion along that path. The barrier to the motion along the path is only ≅ 20 cm-1.

Inter/Intramolecular Bonds in TH5+ (T = C/Si/Ge): H2 as Tetrel Bond Acceptor and the Uniqueness of Carbon Bonds.

Atoms in molecules (AIM), natural bond orbital (NBO), and normal coordinate analysis have been carried out at the global minimum structures of TH5+ (T = C/Si/Ge). All these analyses lead to a consistent structure for these three protonated TH4 molecules. The CH5+ has a structure with three short and two long C-H covalent bonds and no H-H bond. Hence, the popular characterization of protonated methane as a weakly bound CH3+ and H2 is inconsistent with these results. However, SiH5+ and GeH5+ are both indeed a complex formed between TH3+ and H2 stabilized by a tetrel bond, with the H2 being the tetrel bond acceptor. The three-center-two-electron bond (3c-2e) in CH5+ has an open structure, which can be characterized as a V-type 3c-2e bond and that found in SiH5+ and GeH5+ is a T-type 3c-2e bond. This difference could be understood based on the typical C-H, Si-H, Ge-H, and H-H bond and the tetrel bond energies. This analysis explains the trend observed in proton affinity of TH4 which appears counterintuitive, GeH4 > SiH4 > CH4. Carbon is selective in forming a "tetrel bond" and when it does, it might be worthwhile to highlight it as a "carbon bond".

The H2 S Dimer is Hydrogen-Bonded: Direct Confirmation from Microwave Spectroscopy.

Ice and solid H2 S look as different as pears and oranges, leading Pauling to conclude that H2 O has hydrogen bonds and H2 S has van der Waals interactions. Now it is shown that the H2 S dimer, like the H2 O dimer, is indeed hydrogen-bonded.

H2O-CH4 and H2S-CH4 complexes: a direct comparison through molecular beam experiments and ab initio calculations.

New molecular beam scattering experiments have been performed to measure the total (elastic plus inelastic) cross sections as a function of the velocity in collisions between water and hydrogen sulfide projectile molecules and the methane target. Measured data have been exploited to characterize the range and strength of the intermolecular interaction in such systems, which are of relevance as they drive the gas phase molecular dynamics and the clathrate formation. Complementary information has been obtained by rotational spectra, recorded for the hydrogen sulfide-methane complex, with a pulsed nozzle Fourier transform microwave spectrometer. Extensive ab initio calculations have been performed to rationalize all the experimental findings. The combination of experimental and theoretical information has established the ground for the understanding of the nature of the interaction and allows for its basic components to be modelled, including charge transfer, in these weakly bound systems. The intermolecular potential for H2S-CH4 is significantly less anisotropic than for H2O-CH4, although both of them have potential minima that can be characterized as 'hydrogen bonded'.

Microwave Spectrum of Hexafluoroisopropanol and Torsional Behavior of Molecules with a CF3-C-CF3 Group.

This paper presents the first microwave spectroscopic investigation on hexafluoroisopropanol (HFIP). A pulsed nozzle Fourier transform microwave spectrometer has been used to determine the rotational constants for HFIP as A = 2105.12166(18) MHz, B = 1053.99503(12) MHz, and C = 932.33959(13) MHz. In addition, five isotopologues of HFIP have been observed experimentally to determine the accurate structure of HFIP. The observed spectrum could be assigned to the most stable conformer of HFIP, called antiperiplanar. Available spectroscopic information and ab initio calculations on five prototype molecules helped in exploring the torsional behavior of molecules having a CF3-C-CF3 group. Two-dimensional potential energy surfaces have been analyzed for all molecules, which explained the presence/absence of doubling in the rotational transitions. With the help of natural bond orbital (NBO) analysis, reasons for the conformational preference of HFIP have been explained.

Dynamics of the chemical bond: inter- and intra-molecular hydrogen bond.

In this discussion, we show that a static definition of a 'bond' is not viable by looking at a few examples for both inter- and intra-molecular hydrogen bonding. This follows from our earlier work (Goswami and Arunan, Phys. Chem. Chem. Phys. 2009, 11, 8974) which showed a practical way to differentiate 'hydrogen bonding' from 'van der Waals interaction'. We report results from ab initio and atoms in molecules theoretical calculations for a series of Rg∙∙∙HX complexes (Rg=He/Ne/Ar and X=F/Cl/Br) and ethane-1,2-diol. Results for the Rg∙∙∙HX/DX complexes show that Rg∙∙∙DX could have a 'deuterium bond' even when Rg∙∙∙HX is not 'hydrogen bonded', according to the practical criterion given by Goswami and Arunan. Results for ethane-1,2-diol show that an 'intra-molecular hydrogen bond' can appear during a normal mode vibration which is dominated by the OO stretching, though a 'bond' is not found in the equilibrium structure. This dynamical 'bond' formation may nevertheless be important in ensuring the continuity of electron density across a molecule. In the former case, a vibration 'breaks' an existing bond and in the later case, a vibration leads to 'bond' formation. In both cases, the molecule/complex stays bound irrespective of what happens to this 'hydrogen bond'. Both these cases push the borders on the recent IUPAC recommendation on hydrogen bonding (Arunan et al. Pure. Appl. Chem. 2011, 83 1637) and justify the inclusive nature of the definition.

The X-C···π (X = F, Cl, Br, CN) carbon bond.

High-level ab initio calculations have been used to study the interactions between the CH3 group of CH3X (X = F, Cl, Br, CN) molecules and π-electrons. These interactions are important because of the abundance of both the CH3 groups and π-electrons in biological systems. Complexes between C2H4/C2H2 and CH3X molecules have been used as model systems. Various theoretical methods such as atoms in molecules theory, reduced density gradient analysis, and natural bond orbital analysis have been used to discern these interactions. These analyses show that the interaction of the π-electrons with the CH3X molecules leads to the formation of X-C···π carbon bonds. Similar complexes with other tetrel molecules, SiH3X and GeH3X, have also been considered.

Hydrogen bonding, halogen bonding and lithium bonding: an atoms in molecules and natural bond orbital perspective towards conservation of total bond order, inter- and intra-molecular bonding.

One hundred complexes have been investigated exhibiting D-X···A interactions, where X = H, Cl or Li and DX is the 'X bond' donor and A is the acceptor. The optimized structures of all these complexes have been used to propose a generalized 'Legon-Millen rule' for the angular geometry in all these interactions. A detailed Atoms in Molecules (AIM) theoretical analysis confirms an important conclusion, known in the literature: there is a strong correlation between the electron density at the XA bond critical point (BCP) and the interaction energy for all these interactions. In addition, we show that extrapolation of the fitted line leads to the ionic bond for Li-bonding (electrostatic) while for hydrogen and chlorine bonding, it leads to the covalent bond. Further, we observe a strong correlation between the change in electron density at the D-X BCP and that at the X···A BCP, suggesting conservation of the bond order. The correlation found between penetration and electron density at BCP can be very useful for crystal structure analysis, which relies on arbitrary van der Waals radii for estimating penetration. Various criteria proposed for shared- and closed-shell interactions based on electron density topology have been tested for H/Cl/Li bonded complexes. Finally, using the natural bond orbital (NBO) analysis it is shown that the D-X bond weakens upon X bond formation, whether it is ionic (DLi) or covalent (DH/DCl) and the respective indices such as ionicity or covalent bond order decrease. Clearly, one can think of conservation of bond order that includes ionic and covalent contributions to both D-X and X···A bonds, for not only X = H/Cl/Li investigated here but also any atom involved in intermolecular bonding.

Microwave spectroscopic and atoms in molecules theoretical investigations on the Ar···propargyl alcohol complex: Ar···H-O, Ar···π, and Ar···C interactions.

The structure of the Ar···propargyl alcohol (Ar···PA) complex is determined from the rotational spectra of the parent complex and its two deuterated isotopologues, namely Ar···PA-D(OD) and Ar···PA-D(CD). The spectra confirm a geometry in which PA exists in the gauche form with Ar located in between -OH and -C≡C-H groups. All a, b and c types of transitions show small splitting due to some large-amplitude motion dominated by C-OH torsion, as in the monomer. Splittings in a- and b-type transitions are of the order of a few kilohertz, whereas splitting in the c-type transitions is relatively larger (0.9-2.6 MHz) and decreases in the order Ar···PA>Ar···PA-D(CD)>Ar···PA-D(OD). The assignments are well supported by ab initio calculations. Atoms in molecules (AIM) and electrostatic potential calculations are used to explore the nature of the interactions in this complex. AIM calculations not only reveal the expected O-H···Ar and π···Ar interactions in the Ar···gauche-PA complex, but also novel C···Ar (of CH2OH group) and O-H···Ar interactions in the Ar···trans-PA complex. Similar interactions are also present in the Ar···methanol complex.