Charge-Shift Bonding Propensity in Halogen-Bonded BXY (B Is a Small Lewis Base H2O or NH3; X and Y Are Halogen Atoms) Complexes: An NBO/NRT/AIM Investigation.

Charge-shift (CS) bonding is a new bonding paradigm in the field of chemical bonds. Our recent study has revealed that certain Cu/Ag/Au-bonds display both CS bonding and ω-bonding characters. In this investigation, we extend our study to halogen bonding. Our focus is on scrutinizing the CS bonding in halogen-bonded BXY (B is a small Lewis base H2O or NH3; X and Y are halogen atoms) complexes by using natural bond orbital (NBO) analysis, natural resonance theory (NRT), and atoms in molecules (AIM) methods. The primary objective is to establish a connection between halogen bonding (B-X) in BXY and CS bonding in free XY (di-halogens). The calculations indicate that the studied BXY can be classified into two types. One type with a weak halogen bond shows closed-shell interaction. The other type with a stronger B-X interaction exhibits both CS bonding and ω-bonding characters (as seen in NH3ClF, NH3BrF, and NH3IF). Another interesting finding is a novel propensity that the CS bonding in free XY tends to carry over the halogen bonding in BXY, and the same propensity is found in Cu/Ag/Au ω-bonded species. The present study may offer an approach to probe CS bonding in many more 3c/4e ω-bonded molecules.

Micro- and Nanoencapsulated Hybrid Delivery System (MNEHDS): A Novel Approach for Colon-Targeted Oral Delivery of Berberine.

Berberine (BBR) is currently explored in the oral treatment of many disorders, especially in those involving inflammatory processes. Nanotechnology-based drug delivery systems are emerging as an effective approach for improving the poor oral absorption/bioavailability of BBR. To optimize the BBR immunoregulatory effects on a specific part of the gastrointestinal tract, here we describe a micro- and nanoencapsulated hybrid delivery system (MNEHDS) for colon-targeted oral delivery of BBR and test its therapeutic efficacy in a murine colitis model. The MNEHDS is formed by encapsulation of BBR-loaded poly(lactic-co-glycolic acid) nanoparticles into a pH-sensitive, BBR-pre-entrapped Eudragit FS30D matrix to form a hybrid microparticle composed of the BBR and BBR nanoparticles. Once in the colonic environment, the microencapsulated BBR is almost completely released for immediate action, while BBR nanoparticles can provide sustained release of BBR subsequent to their intestinal absorption. One dose of oral MNEHDS/BBR treatment results in significant attenuation of acute colitis induced by dextran sulfate sodium. The MNEHDS/BBR also proves to be effective during chronically induced colitis with two doses given 1 week apart. The improved efficacy is accompanied by decreased production of colon inflammation. Comparatively, oral treatment with one or two 7-day courses of free BBR has less effect on ameliorating either acute or chronic colitis. Thus, MNEHDS represents a novel delivery system for BBR, and potentially other therapeutic agents, to treat inflammatory bowel disease.

Identification of the New In Vivo Metabolites of Ilaprazole in Rat Plasma after Oral Administration by LC-MS: In Silico Prediction of the H+/K+-ATPase Inhibitor.

Ilaprazole is a proton pump inhibitor used to treat digestive diseases. In this study, blood samples were collected after oral administration of ilaprazole and prepared by liquid-liquid extraction. The metabolites of ilaprazole were detected by liquid chromatography-high-resolution mass spectrometry (LC-HRMS) and LC-MSn. A total of twelve in vivo metabolites were detected in rat plasma and six new metabolites of ilaprazole, including one reductive metabolite with sulfide (M3), two hydroxylated metabolites with sulfoxide (M7 and M8), and three oxidative metabolites with sulfone (M9, M11, and M12), were identified. The possible metabolic pathways of ilaprazole and the fragmentation behaviors of its metabolites were elucidated. The result of the in silico prediction indicates that all the new metabolites showed the potential ability to inhibit H+/K+-ATPase activity.

Understanding and modulating the high-energy properties of noble-gas hydrides from their long-bonding: an NBO/NRT investigation on HNgCO+/CS+/OSi+ and HNgCN/NC (Ng = He, Ar, Kr, Xe, Rn) molecules.

The noble-gas hydrides, HNgX (X is an electronegative atom or fragment), represent potential high-energy materials because their two-body decomposition process, HNgX → Ng + HX, is strongly exoergic. Our previous studies have shown that each member of the HNgX (X = halogen atom or CN/NC fragment) molecules is composed of three leading resonance structures: two ω-bonding structures (H-Ng+ :X- and H:- Ng+-X) and one long-bonding structure (H∧X). The last one paints a novel [small sigma, Greek, circumflex]-type long-bonding picture. The present study focuses on the relationship between this novel bonding motif and the unusual energetic properties. We chose HNgCO+/CS+/OSi+/CN/NC, with the formula HNgAB (Ng = He, Ar, Kr, Xe, Rn; AB = CO+/CS+/OSi+/CN/NC) as the research system. We first investigated the bonding of HNgCO+ and its analogous HNgCS+/OSi+ species using NBO/NRT methods, and quantitatively compared the bonding with that in HNgCN/NC molecules. NBO/NRT results showed that each of the HNgCO+/CS+/OSi+ molecules could be better represented as a resonance hybrid of ω-bonding and long-bonding structures, but the long-bonding is much weaker than that in HNgCN/NC molecules. Furthermore, we introduced the long-bonding concept into the rationalization of the high-energy properties, and found a good correlation between the highly exothermic two-body dissociation channel and the long-bond order, bH-A. We also found that the long-bond order is highly tunable for these noble-gas hydrides due to its dependence on the nature of the electronegative AB fragments or the central noble-gas atoms, Ng. On the basis of these results, we could optimize the energetic properties by changing the long-bonding motif of our studied molecules. Overall, this study shows that the long-bonding model provides an easy way to rationalize and modulate the unusual energy properties of noble-gas hydrides, and that it is helpful to predict some noble-gas hydrides as potential energetic materials.

Long-Bonding in HNgCN/NC (Ng = Noble Gas) Molecules: An NBO/NRT Investigation.

Recently, Weinhold et al. put forward one new concept of σ̂-type long-bonding and applied it to the comprehension of halogen noble-gas hydrides HNgY (Ng = noble gas; Y = halogen) bonding. The present study extends this new concept into HNgX (X = CN, NC) pseudohalogen molecules. At the B3LYP and CCSD(T) levels of theory, we perform natural bond orbital (NBO) and natural resonance theory (NRT) studies on the HNgX molecules and compare them with the previous results for HNgY molecules. The NBO/NRT results clearly reveal that each of the HNgX, but not the HHeCN, HNeCN, and HNeNC molecules, is composed of three leading resonance structures: two ω-bonding structures H-Ng+:X-, H:-Ng+-X and one long-bonded structure H∧X. This result indicates that the conventional long-bonding exists in these pseudohalogen molecules, like the long-bonding in HNgY molecules. Unexpectedly, we identify a new type of longer long-bonded structure H∧C in HNeNC molecule at the B3LYP level, which disappears at the CCSD level. This misleading prediction at the B3LYP level can be traced back to the singlet diradical character, which induces a low-quality geometry. Therefore, the geometry reoptimization of the noble-gas hydrides is indispensable using CASSCF-based methods, if the noble-gas hydrides fail the "Stable" test because of diradical-type instability.

Insight into the Bonding Mechanism and the Bonding Covalency in Noble Gas-Noble Metal Halides: An NBO/NRT Investigation.

The bonding between noble gas and noble metal halide like hydrogen bonding (H-bonding) motivates us to investigate the bonding mechanism and the bonding covalency in NgMX (Ng = He, Ne, Ar, Kr, Xe, Rn; M = Cu, Ag, Au; X = F, Cl, Br, I) complexes using natural bond orbital (NBO) and natural resonance theory (NRT) methods. In this study, we introduce the new resonance bonding model in H-bonding into NgMX bonding. We provide strong evidence for resonance bonding involving two important resonance structures: Ng: M-X ↔ Ng+-M :X- in each of NgMX complexes, originating in the nNg → σ*MX hyperconjugative interaction. The covalency of the bonding could be understood by the localized nature of Ng-M bonds in these two resonance structures, and the degree of Ng-M covalency can be quantitatively described by calculated NRT bond orders bNgM. Furthermore, we find that the bond order satisfies conservation of bond order, bNgM + bMX = 1, for all of the studied complexes. On the basis of the conservation of bond order and some statistical correlations, we also reveal that the Ng-M bond (except He-Ag and Ne-Ag bonds) can be tuned by changing the auxiliary ligand X. Overall, the present studies provide new insight into the bonding mechanism and the covalency of the bonding in noble gas-noble metal halides, and develop one resonance bonding model.

3c/4e [small sigma, Greek, circumflex]-type long-bonding competes with ω-bonding in noble-gas hydrides HNgY (Ng = He, Ne, Ar, Kr, Xe, Rn; Y = F, Cl, Br, I): a NBO/NRT perspective.

Noble-gas hydrides HNgY are frequently described as a single ionic form (H-Ng)(+)Y(-). We apply natural bond orbital (NBO) and natural resonance theory (NRT) analyses to a series of noble-gas hydrides HNgY (Ng = He, Ne, Ar, Kr, Xe, Rn; Y = F, Cl, Br, I) to gain quantitative insight into the resonance bonding of these hypervalent molecules. We find that each of the studied species should be better represented as a resonance hybrid of three leading resonance structures, namely, H-Ng(+ -):Y (I), H:(- +)Ng-Y (II), and H^Y (III), in which the "ω-bonded" structures I and II arise from the complementary donor-acceptor interactions nY → σ*HNg and nH → σ*NgY, while the "long-bond" ([small sigma, Greek, circumflex]-type) structure III arises from the nNg → [small sigma, Greek, circumflex]*HY/[small sigma, Greek, circumflex]HY interaction. The bonding for all of the studied molecules can be well described in terms of the continuously variable resonance weightings of 3c/4e ω-bonding and [small sigma, Greek, circumflex]-type long-bonding motifs. Furthermore, we find that the calculated bond orders satisfy a generalized form of "conservation of bond order" that incorporates both ω-bonding and long-bonding contributions [viz., (bHNg + bNgY) + bHY = bω-bonding + blong-bonding = 1]. Such "conservation" throughout the title series implies a competitive relationship between ω-bonding and [small sigma, Greek, circumflex]-type long-bonding, whose variations are found to depend in a chemically reasonable manner on the electronegativity of Y and the outer valence-shell character of the central Ng atom. The calculated bond orders are also found to exhibit chemically reasonable correlations with bond lengths, vibrational frequencies, and bond dissociation energies, in accord with Badger's rule and related empirical relationships. Overall, the results provide electronic principles and chemical insight that may prove useful in the rational design of noble-gas hydrides of technological interest.

Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋠⋠⋠M-X (X=F, Cl, Br, CH3, CF3) Complexes.

The resonance character of Cu/Ag/Au bonding is investigated in B⋅⋅⋅M-X (M=Cu, Ag, Au; X=F, Cl, Br, CH3, CF3; B=CO, H2O, H2S, C2H2, C2H4) complexes. The natural bond orbital/natural resonance theory results strongly support the general resonance-type three-center/four-electron (3c/4e) picture of Cu/Ag/Au bonding, B:M-X↔B(+) -M:X(-) , which mainly arises from hyperconjugation interactions. On the basis of such resonance-type bonding mechanisms, the ligand effects in the more strongly bound OC⋅⋅⋅M-X series are analyzed, and distinct competition between CO and the axial ligand X is observed. This competitive bonding picture directly explains why CO in OC⋅⋅⋅Au-CF3 can be readily replaced by a number of other ligands. Additionally, conservation of the bond order indicates that the idealized relationship bB⋅⋅⋅M +bMX =1 should be suitably generalized for intermolecular bonding, especially if there is additional partial multiple bonding at one end of the 3c/4e hyperbonded triad.

Dual bonding between H2O/H2S and AgCl/CuCl: Cu/Ag bond, sister bond to Au bond.

Recently, Legon et al. reported the first generation and characterization of H2O/H2S···AgCl complexes by rotational spectroscopy and proposed whether there is a silver bond analogous to the more familiar hydrogen and halogen bonds. In this study, a theoretical investigation was performed to answer this question and to deepen the nature of intermolecular interactions for H2O/H2S···M-Cl (M = Cu, Ag, and Au) complexes. NBO analyses reveal that two types of delocalization interactions coexist in these complexes. Apart from the expected σ-donation interaction, the hyperconjugation interaction between H2O/H2S and M-Cl also takes part in the bonding. On the basis of such a dual-bonding mechanism, one class of bond, termed Cu/Ag bond, was defined in this study. In addition, the topological properties at a bond critical point, binding energies, and stretching frequency shifts studied here support that Cu/Ag bond is a sister bond to Au bond put forward previously by Sadlej et al. The Cu/Ag/Au bond is partially covalent and partially electrostatic in nature. Finally, the dual-bonding mechanism of Cu/Ag/Au bond was further discussed. This dual-bonding scheme may be considered a new synergistic bonding model for coordination compounds.

Equivalent and Complement of the ω-Bonding Model and Charge-Shift Bonding Model: A Natural Bond Orbital/Natural Resonance Theory/Atoms in Molecules Investigation via Cu/Ag/Au Bonding in BMX (B = H2O, H2S, NH3, and PH3; M = Cu, Ag, and Au; and X = F, Cl, Br, and I).

Chemical bonding is the language of logic for chemists. Two new resonance bonding models, ω-bonding and charge-shift (CS) bonding, are gaining popularity among chemists. This study investigated the Cu/Ag/Au bonding in BMX (B = H2O, H2S, NH3, and PH3; M = Cu, Ag, and Au; and X = F, Cl, Br, and I) complexes using natural bond orbital (NBO) analysis, natural resonance theory (NRT), and atoms in molecules (AIM) method. The main aim is to reveal the relation between ω-bonding model and CS bonding model via Cu/Ag/Au bonding. Our studies demonstrate that the Cu/Ag/Au bonds exhibit the characteristics of both ω-bonding and CS bonding. Further studies found that ω-bonding and CS bonding models are equivalent and complement each other in understanding the studied Cu/Ag/Au bonding. Another interesting finding is the implication of the omega symbol in the ω-bonding model. These findings could help to promote the communication and CS bonding understanding of many more similar ω-bonded complexes.

Enantioselectivity in organocatalytic cascade double Michael addition reaction: a theoretical study.

We have investigated important intermediates and key transition states of the organocatalyzed cascade double Michael addition using density functional theory. The calculated results suggest that the reaction contains intermolecular nucleophilic addition and intramolecular cyclization, both involving the formation of two stereocenters. The iminium-enamine catalysis of secondary amine unit enables the cascade addition to proceed consecutively. As an electron transport, the iminium attracts the electron stream to promote the nucleophilic addition. Then enamine causes the electron stream to catalyze the cyclization. As H bond donor, the catalyst forms three types of C-H···O H bond with substrates. The enantioselectivity and diastereoselectivity are dominated by the catalyst backbone. Two group links of pyrrole-phenyl and pyrrole-silyl ether orient the reaction in paths with smaller rotations of the linked single bonds. Our conclusion is supported by NBO analysis and the predicted ee, dr values according to the experiment.

The C3-bending vibrational levels of the C3-Kr and C3-Xe van der Waals complexes studied by their Ã-X̃ electronic transitions and by ab initio calculations.

Fluorescence excitation spectra and wavelength-resolved emission spectra of the C(3)-Kr and C(3)-Xe van der Waals (vdW) complexes have been recorded near the 2(2-)(0), 2(2+)(0), 2(4-)(0), and 1(1)(0) bands of the Ã(1)Π(u)-X̃(1)Σ(g)(+) system of the C(3) molecule. In the excitation spectra, the spectral features of the two complexes are red-shifted relative to those of free C(3) by 21.9-38.2 and 34.3-36.1 cm(-1), respectively. The emission spectra from the à state of the Kr complex consist of progressions in the two C(3)-bending vibrations (ν(2), ν(4)), the vdW stretching (ν(3)), and bending vibrations (ν(6)), suggesting that the equilibrium geometry in the X̃ state is nonlinear. As in the Ar complex [Zhang et al., J. Chem. Phys. 120, 3189 (2004)], the C(3)-bending vibrational levels of the Kr complex shift progressively to lower energy with respect to those of free C(3) as the bending quantum number increases. Their vibrational structures could be modeled as perturbed harmonic oscillators, with the dipole-induced dipole terms of the Ar and Kr complexes scaled roughly by the polarizabilities of the Ar and Kr atoms. Emission spectra of the Xe complex, excited near the Ã, 2(2-) level of free C(3), consist only of progressions in even quanta of the C(3)-bending and vdW modes, implying that the geometry in the higher vibrational levels (υ(bend) ≥ 4, E(vib) ≥ 328 cm(-1)) of the X̃ state is (vibrationally averaged) linear. In this structure the Xe atom bonds to one of the terminal carbons nearly along the inertial a-axis of bent C(3). Our ab initio calculations of the Xe complex at the level of CCSD(T)∕aug-cc-pVTZ (C) and aug-cc-pVTZ-PP (Xe) predict that its equilibrium geometry is T-shaped (as in the Ar and Kr complexes), and also support the assignment of a stable linear isomer when the amplitude of the C(3) bending vibration is large (υ(4) ≥ 4).

Pharmacokinetic Comparisons of Naringenin and Naringenin-Nicotinamide Cocrystal in Rats by LC-MS/MS.

Naringenin (NAR), 4',5,7-trihydroxydihydroflavone, has a wide range of pharmacological activities but shows poor water solubility and low bioavailability. The pharmacokinetics and bioavailability of naringenin-nicotinamide cocrystal (NAR-NCT), which offers improved solubility, were evaluated in this study. Rats were orally administered NAR, a physical mixture of naringenin and nicotinamide (NAR + NCT), and NAR-NCT. The relative bioavailability of NAR-NCT was 175.09% of NAR, Cmax was 8.43 and 2.06 times of NAR and NAR + NCT, respectively, Tmax was advanced from 0.49 h to 0.09 h, CL was decreased from 91.1 L/h/kg to 49.1 L/h/kg, and t 1/2 was increased from 5.37 h to 8.24 h, highlighting its rapid absorption and slow elimination. This study showed that NAR-NCT could improve the bioavailability of NAR.

Charge-Shift Bonding in Xenon Hydrides: An NBO/NRT Investigation on HXeY···HX (Y = Cl, Br, I; X = OH, Cl, Br, I, CCH, CN) via H-Xe Blue-Shift Phenomena.

Noble-gas bonding represents curiosity. Some xenon hydrides, such as HXeY (Y = Cl, Br, I) and their hydrogen-bonded complexes HXeY···HX (Y = Cl, Br, I; X = OH, Cl, Br, I, CN, CCH), have been identified in matrixes by observing H-Xe frequencies or its monomer-to-complex blue shifts. However, the H-Xe bonding in HXeY is not yet completely understood. Previous theoretical studies provide two answers. The first one holds that it is a classical covalent bond, based on a single ionic structure H-Xe+ Y-. The second one holds that it is resonance bonding between H-Xe+ Y- and H- Xe+-Y. This study investigates the H-Xe bonding, via unusual blue-shifted phenomena, combined with some NBO/NRT calculations for chosen hydrogen-bonded complexes HXeY···HX (Y = Cl, Br, I; X = OH, Cl, Br, I, CN, CCH). This study provides new insights into the H-Xe bonding in HXeY. The H-Xe bond in HXeY is not a classical covalent bond. It is a charge-shift (CS) bond, a new class of electron-pair bonds, which is proposed by Shaik and Hiberty et al. The unusual blue shift in studied hydrogen-bonded complexes is its H-Xe CS bonding character in IR spectroscopy. It is expected that these studies on the H-Xe bonding and its IR spectroscopic property might assist the chemical community in accepting this new-class electron-pair bond concept.

Resonance bonding in XNgY (X = F, Cl, Br, I; Ng = Kr or Xe; Y = CN or NC) molecules: an NBO/NRT investigation.

Several noble-gas-containing molecules XNgY were observed experimentally. However, the bonding in such systems is still not understood. Using natural bond orbital and natural resonance theory (NBO/NRT) methods, the present work investigated bonding of the title molecules. The results show that each of the studied XNgY molecules should be better described as a resonance hybrid of ω-bonding and [Formula: see text]-type long-bonding structures: X:- Ng+ - Y, X - Ng+: Y-, and X^Y. The ω-bonding and long-bonding make competing contributions to the composite resonance hybrid due to the accurately preserved bond order conservation principle. We find that the resonance bonding is highly tunable for these noble-gas-containing molecules due to its dependence on the nature of the halogen X or the central noble-gas atoms Ng. When the molecule XNgY consists of a relatively lighter Ng atom, a relatively low-electronegative X atom, and the CN fragment rather than NC, the long-bonding structure X^Y tends to be highlighted. In contrast, the heavy Ng atom and high-electronegative X atom will enhance the ω-bonding structure. Overall, the present work provides electronic principles and chemical insights that help understand the bonding in these XNgY species.

Ligand effects due to resonance character in LAuCCH(-) (L = F, Cl, Br, I, CCH) complexes: an NBO/NRT analysis.

The organogold complexes of LAuCCH(-) (L = F, Cl, Br, I, CCH) were investigated using natural bond orbital/natural resonance theory (NBO/NRT) methods. The NBO/NRT results strongly support the general resonance-type three-center-four-electron (3c/4e) picture of LAuCCH: L(-): Au-CCH ↔ L-Au :CCH(-), arising from hyperconjugation interactions. The sums of ionic and covalent contributions to both L-Au and Au-CCH bonds are all slightly larger than that due to the additional π-back bonding within the 3c/4e hyperbonded triad. This complementary relationship between L-Au and Au-CCH bond orders implies a competing relationship between the ancillary ligand and CCH around the gold atom. We discuss the ligand effects in the LAuCCH(-) series on the basis of this competing relationship.

π-π Stacking and ferromagnetic coupling mechanism on a binuclear Cu(II) complex.

The ferromagnetic couplings were observed in an unpublished crystal that consists of binuclear copper(II) complexes, namely, [Cu(2)(µ(1,3)-SCN)(2)(PhenOH)(OCH(3))(2)(HOCH(3))(2)] (PhenOH = 2-hydroxy-1,10-phenanthroline), and in the binuclear complex Cu(ii) ion assumes a distorted octahedral geometry and thiocyanate anion functions as a µ(1,3)-SCN(-) equatorial-axial (EA) bridging ligand. The analysis for the crystal structure indicates that there are three types of magnetic coupling pathways, in which two pathways involve π-π stacking between the adjacent complexes and the third one is the µ(1,3)-SCN(-) bridged pathway. The fitting for the data of the variable-temperature magnetic susceptibilities shows that there is a ferromagnetic coupling between adjacent Cu(II) ions with J = 50.02 cm(-1). Theoretical calculations reveal that the two types of π-π stacking resulted in ferromagnetic couplings with J = 4.16 cm(-1) and J = 2.75 cm(-1), respectively, and the bridged thiocyanate anions pathway led to a weaker ferromagnetic interaction with J = 0.88 cm(-1). The theoretical calculations also indicate that the ferromagnetic coupling sign from the two types of π-π stacking does not accord with McConnell I spin-polarization mechanism. The analysis for the Wiberg bond indexes that originate from the π-π stacking atoms indicates that the Wiberg bond indexes are relevant to the associated magnetic coupling magnitude and the Wiberg bond index is one of the key factors that dominates the associated magnetic coupling magnitude.

On the mechanism of carbonyl hydrogenation catalyzed by iron catalyst.

Density functional theory calculations have been performed to investigate the detailed mechanism of the carbonyl hydrogenation catalyzed by the first well-defined bifunctional iron catalyst. The catalytic reaction proceeds by hydrogen transfer and dihydrogen activation. The hydrogen transfer reaction occurs via the bifunctional mechanism in which the two hydrogen atoms attached on the Fe and O of the catalyst are transferred to the oxygen and carbon atom of the carbonyl compound concertedly. Both the alcohol-mediated and nonalcohol-mediated dihydrogen activation processes are explored.

The 4051-Angstroms band of C3 (A 1Piu-X 1Sigmag +, 000-000): perturbed low-J lines and lifetime measurements.

Rotational analyses have been carried out at high resolution for the 000-000 and 000-100 bands of the A (1)Pi(u)-X (1)Sigma(g) (+) transition of supersonic jet-cooled C(3). Two different spectra have been recorded for each band, using time gatings of 20-150 and 800-2300 ns. At the shorter time delay the spectra show only the lines observed by many previous workers. At the longer time delay many extra lines appear, some of which have been observed previously by [McCall et al.Chem. Phys. Lett. 374, 583 (2003)] in cavity ring-down spectra of jet-cooled C(3). Detailed analysis of these extra lines shows that at least two long-lived states perturb the A (1)Pi(u), 000 state. One of these appears to be a (3)Sigma(u) (-) vibronic state, which may possibly be a high vibrational level of the b (3)Pi(g) state, and the other appears to be a P = 1 state with a low rotational constant B. Our spectra also confirm the reassignment by McCall et al. of the R(0) line of the 000-000 band, which is consistent with the spectra recorded towards a number of stars that indicate the presence of C(3) in the interstellar medium. Fluorescence lifetimes have been measured for a number of upper-state rotational levels. The rotational levels of the A (1)Pi(u) state have lifetimes in the range of 230-190 ns, decreasing slightly with J; the levels of the perturbing states have much longer lifetimes, with some of them showing biexponential decays. An improved value has been obtained for the nu(1) vibrational frequency of the ground state, nu(1) = 1224.4933 +/- 0.0029 cm(-1).

The C3-bending levels of the C3-Ar complex studied by optical spectroscopy and ab initio calculation.

The A-X electronic transition of C3-Ar, near 405 nm, has been studied by both laser-induced fluorescence and wavelength-resolved emission techniques. Emission spectra have been recorded from 14 vibrational levels of the A state of C3-Ar; these spectra consist of progressions in the ground state v2 and v4 vibrations (the in- and out-of-plane C3-bending motions, respectively). With increasing bending excitation, these ground state levels shift progressively downwards compared to those of free C3, indicating that the van der Waals complexes are becoming more tightly bound. The level structure of the two vibrations of C3-Ar has been fitted to a perturbed harmonic oscillator model, where the potential function has the form V = V1r cos theta + V2r2 cos 2theta (r is the amplitude of the C3-bending motion and theta gives the orientation of the rare gas atom relative to the plane of the bent C3 molecule). Ab initio calculations have been carried out for C3-Ar at the coupled-cluster singles, doubles (and triples)/correlation consistent polarization valence quadruple-zeta level. They predict that the C3-Ar complex is nearly T shaped at equilibrium, and that as the C3 molecule bends away from the linear configuration, the preferred orientation is "arrow" shaped. From the results of the best fit to the model and the emission spectral intensities, the relative orientation of the out-of-plane pi electron of the A-state complex and the Ar atom has been estimated. No bands of the Ar complex were found near the C3, A-X, (0,0) band, consistent with the fact that the A 1Piu, upsilon = 0 level of free C3 is strongly perturbed by triplet levels. In the excitation spectra of the Ar complex, the bands with upsilonb' > 0 show redshifts of about 16-36 cm(-1) compared to those of free C3, indicating that the A-state complex in these levels is more tightly bonded than the X-state complex.