Spectroscopic identification of oxonium and carbenium ions of protonated phenol in the gas phase: IR spectra of weakly bound C6H7O+ -L dimers (L = Ne, Ar, N2)

Structural isomers of isolated protonated phenol (C(6)H(7)O(+)) are characterized by infrared (IR) photodissociation spectroscopy of their weakly bound complexes with neutral ligands L (L = Ne, Ar, N(2)). IR spectra of C(6)H(7)O(+)-L recorded in the vicinity of the O-H and C-H stretch fundamentals carry unambiguous signatures of at least two C(6)H(7)O(+) isomers: the identified protonation sites of phenol include the O atom (oxonium ion, O-C(6)H(7)O(+)) and the C atoms of the aromatic ring in the ortho and/or para position (carbenium ions, o/p-C(6)H(7)O(+)). In contrast, protonation at the meta and ipso positions is not observed. The most stable C(6)H(7)O(+)-L dimer structures feature intermolecular H-bonds between L and the OH groups of O-C(6)H(7)O(+) and o/p-C(6)H(7)O(+). Extrapolation to zero solvation interaction yields reliable experimental vibrational frequencies of bare O-C(6)H(7)O(+) and o/p-C(6)H(7)O(+). The interpretation of the C(6)H(7)O(+)-L spectra, as well as the extrapolated monomer frequencies, is supported by B3LYP and MP2 calculations using the 6-311G(2df,2pd) basis. The spectroscopic and theoretical results elucidate the effect of protonation on the structural properties of phenol and provide a sensitive probe of the activating and ortho/para directing nature of the OH group observed in electrophilic aromatic substitution reactions.     

Isomer-selective detection of microsolvated oxonium and carbenium ions of protonated phenol: infrared spectra of C6H7O+-Ln clusters (L=Ar/N2, n</=6)

Infrared photodissociation (IRPD) spectra of clusters composed of protonated phenol (C(6)H(7)O(+)) and several ligands L are recorded in the O-H and C-H stretch ranges using a tandem mass spectrometer coupled to a cluster ion source. The C(6)H(7)O(+)-L(n) complexes (L=Ar/N(2), n=1-6) are generated by chemical ionization of a supersonic expansion. The IRPD spectra of mass selected C(6)H(7)O(+)-L(n) clusters obtained in various C(6)H(7)O(+)-L(m) fragment channels (m相似文献   

Hydrogen-bonded networks in ethanol proton wires: IR spectra of (EtOH)qH+-Ln clusters (L = Ar/N2, q < or = 4, n < or = 5)

Isolated and microsolvated protonated ethanol clusters, (EtOH)qH+-Ln with L = Ar and N2, are characterized by infrared photodissociation (IRPD) spectroscopy in the 3 microm range and quantum chemical calculations. For comparison, also the spectrum of the protonated methanol dimer, (MeOH)2H+, is presented. The IRPD spectra carry the signature of H-bonded (EtOH)qH+ chain structures, in which the excess proton is either strongly localized on one or (nearly) equally shared between two EtOH molecules, corresponding to Eigen-type ion cores (EtOH2+ for q = 1, 3) or Zundel-type ion cores (EtOH-H+-HOEt for q = 2, 4), respectively. In contrast to neutral (EtOH)q clusters, no cyclic (EtOH)qH+ isomers are detected in the size range investigated (q < or = 4), indicative of the substantial impact of the excess proton on the properties of the H-bonded ethanol network. The acidity of the two terminal OH groups in the (EtOH)qH+ chains decreases with the length of the chain (q). Comparison between (ROH)qH+ with R = CH3 and C2H5 shows that the acidity of the terminal O-H groups increases with the length of the aliphatic rest (R). The most stable (EtOH)qH+-Ln clusters with n < or = 2 feature intermolecular H-bonds between the inert ligands and the two available terminal OH groups of the (EtOH)qH+ chain. Asymmetric microsolvation of (EtOH)qH+ with q = 2 and 4 promotes a switch from Zundel-type to Eigen-type cores, demonstrating that the fundamental structural motif of the (EtOH)qH+ proton wire sensitively depends on the environment. The strength of the H-bonds between L and (EtOH)qH+ is shown to provide a rather sensitive probe of the acidity of the terminal OH groups.     

Interaction of ionic biomolecular building blocks with nonpolar solvents: acidity of the imidazole cation (Im+) probed by IR spectra of Im+-Ln complexes (L = Ar, N2; n < or = 3)

The intermolecular interaction between the imidazole cation (Im+ = C3N2H4+) and nonpolar ligands is characterized in the ground electronic state by infrared photodissociation (IRPD) spectroscopy of size-selected Im+-Ln complexes (L = Ar, N2) and quantum chemical calculations performed at the UMP2/6-311G(2df,2pd) and UB3LYP/6-311G(2df,2pd) levels of theory. The complexes are created in an electron impact cluster ion source, which predominantly produces the most stable isomers of a given cluster ion. The analysis of the size-dependent frequency shifts of both the N-H and the C-H stretch vibrations and the photofragmentation branching ratios provides valuable information about the stepwise microsolvation of Im+ in a nonpolar hydrophobic environment, including the formation of structural isomers, the competition between various intermolecular binding motifs (H-bonding and pi-bonding) and their interaction energies, and the acidity of both the CH and NH protons. In line with the calculations, the IRPD spectra show that the most stable Im+-L dimers feature planar H-bound equilibrium structures with nearly linear H-bonds of L to the acidic NH group of Im+. Further solvation occurs at the aromatic ring of Im+ via the formation of intermolecular pi-bonds. Comparison with neutral Im-Ar demonstrates the drastic effect of ionization on the topology of the intermolecular potential, in particular in the preferred aromatic substrate-nonpolar recognition motif, which changes from pi-bonding to H-bonding. .     

Microwave spectra, structure, and dynamics of the weakly bound complex, N2 CO2

The Fourier transform microwave spectra of the various isotopologs of the weakly bound complex of carbon dioxide with the most abundant molecule in the atmosphere, nitrogen, have been measured. The structure of the complex has been determined and evidence for the inversion of the N(2) is presented. The molecule is T-shaped, with the OCO forming the cross of the T, a structure consistent with that deduced from a previous rotationally resolved infrared experiment. A significant wide-amplitude bending motion of the N(2) is deduced from the values of the (nearly identical) nuclear quadrupole coupling constants of the nitrogen nuclei. The spectroscopic results are compared with high-quality ab initio calculations. We examine the consequences of the N(2) CO(2) complex formation in the atmosphere upon the greenhouse warming potential of carbon dioxide.     

An ab initio investigation on (CO2)n and CO2(Ar)m clusters: geometries and IR spectra

An ab initio investigation on CO(2) homoclusters is done at MPWB1K6-31++G(2d) level of theory. Electrostatic guidelines are found to be useful for generating initial structures of (CO(2))(n) clusters. The ab initio minimum energy geometries of (CO(2))(n) with n=2-8 are T shaped, cyclic, trigonal pyramidal, tetragonal pyramidal, tetragonal bipyramidal, pentagonal bipyramidal, and pentagonal bipyramid with one CO(2) molecule attached to it. A test calculation on (CO(2))(20) cluster is also reported. The geometric parameters of the energetically most favored (CO(2))(n) clusters match quite well their experimental counterparts (wherever available) as well as those derived from molecular dynamics studies. The effect of clustering is quantified through the asymmetric C-O stretching frequency shift relative to the single CO(2) molecule. (CO(2))(n) clusters show an increasing blueshift from 1.8 to 9.6 cm(-1) on increasing number of CO(2) molecules from n=2 to 8. The energetics and geometries of CO(2)(Ar)(m) clusters have also been explored at the same level of theory. The geometries for m=1-6 show a predominant T type of the argon-CO(2) molecule interaction. Higher clusters with m=7-12 show that the argon atoms cluster around the oxygen atom after the saturation of the central carbon atom. The CO(2)(Ar)(m) clusters exhibit an increasing redshift in the C-O asymmetric stretch relative to CO(2) molecule of 0.7-5.6 cm(-1) with increasing number of argon atoms through m=1-8.     

Infrared spectra of seeded hydrogen clusters: (paraH2)N - OCS, (orthoH2)N - OCS, and (HD)N - OCS, N = 2 - 7

Infrared spectra of hydrogen-carbonyl sulfide clusters containing paraH2, orthoH2, or HD have been studied in the 2060 cm(-1) region of the C-O stretching vibration. The clusters were formed in pulsed supersonic jet expansions and probed using a tunable infrared diode laser spectrometer. Simple symmetric rotor type spectra were observed and assigned for clusters containing up to N = 7 hydrogen molecules. There was no resolved K structure, and Q-branch features were present for orthoH2 and HD but absent for paraH2. These characteristics can be rationalized in terms of near symmetric rotor structures, very low effective rotational temperatures (0.15 to 0.6 K), and nuclear spin statistics. The observed vibrational shifts were compared with those from recent observations on the same clusters embedded in helium nanodroplets. The observed rotational constants for the paraH2 clusters are in good agreement with a recent quantum Monte Carlo simulation. Some mixed clusters were also observed, such as HD-HD-He-OCS and paraH2 - orthoH2 - OCS.     

Infrared spectroscopic investigation of two isomers of the weakly bound complex OCS-(CO2)2

Vibration-rotation spectra of the OCS-(CO(2))(2) van der Waals complex were studied by means of direct infrared absorption spectroscopy. Complexes were generated in a supersonic slit-jet apparatus, and the expansion gas was probed using a rapid-scan tunable diode laser. Infrared bands were observed for two different isomeric forms of the complex. A relatively strong band centered at 2058.799 cm(-1) was assigned to the most stable isomer, which has a barrel-shaped geometry and is already known from microwave spectroscopy. A weaker infrared band centered at 2050.702 cm(-1) was assigned to a new isomeric form, observed here for the first time, which was expected on the basis of ab initio calculations. Infrared bands for seven isotopomers were recorded in an attempt to quantify the structure of the new isomer. Because it has no symmetry elements, nine parameters are needed to fully define the geometry. It was possible to determine six of these which define the relative position of the OCS monomer with respect to the CO(2) dimer fragment in the complex while the remaining three were fixed at their ab initio values. Similarities and differences between the faces of the two isomers of OCS-(CO(2))(2) and the associated dimers are discussed.     

Interaction of the Benzenium Ion with Inert Ligands: IR Spectra of C6H7+?Ln Cluster Cations (L=Ar,N2, CH4, H2O)

IR photodissociation spectra of mass‐selected clusters composed of protonated benzene (C₆H₇⁺) and several ligands L are analyzed in the range of the C? H stretch fundamentals. The investigated systems include C₆H₇⁺? Ar, C₆H₇⁺? (N₂)_n (n=1–4), C₆H₇⁺? (CH₄)_n (n=1–4), and C₆H₇⁺? H₂O. The complexes are produced in a supersonic plasma expansion using chemical ionization. The IR spectra display absorptions near 2800 and 3100 cm^?1, which are attributed to the aliphatic and aromatic C? H stretch vibrations, respectively, of the benzenium ion, that is, the σ complex of C₆H₇⁺. The C₆H₇⁺? (CH₄)_n clusters show additional C? H stretch bands of the CH₄ ligands. Both the frequencies and the relative intensities of the C₆H₇⁺ absorptions are nearly independent of the choice and number of ligands, suggesting that the benzenium ion in the detected C₆H₇⁺? L_n clusters is only weakly perturbed by the microsolvation process. Analysis of photofragmentation branching ratios yield estimated ligand binding energies of the order of 800 and 950 cm^?1 (≈9.5 and 11.5 kJ mol^?1) for N₂ and CH₄, respectively. The interpretation of the experimental data is supported by ab initio calculations for C₆H₇⁺? Ar and C₆H₇⁺? N₂ at the MP 2/6‐311 G(2df,2pd) level. Both the calculations and the spectra are consistent with weak intermolecular π bonds of Ar and N₂ to the C₆H₇⁺ ring. The astrophysical implications of the deduced IR spectrum of C₆H₇⁺ are briefly discussed.     

Electronic absorption spectra of the protonated polyacetylenes H2CnH+ (n = 4, 6, 8) in neon matrixes

Electronic absorption spectra of the protonated polyacetylenic chains H2CnH+ (n = 4, 6, 8) and the neutral H2C8H have been observed in 6 K neon matrixes after mass selection. The wavelength of the H2CnH+ electronic transitions depends quasi-linearly on n, typical of carbon chains. The origin band is at 286.0, 378.6, and 467.6 nm for n = 4, 6, and 8, respectively. Two ground-state vibrations of H2C4H+ in the IR absorption spectrum were also detected. On the basis of the spectroscopic trends and the assignment of the vibrational frequencies in the ground and excited electronic states, it is concluded that the H2CnH+ species are C(2v) linear carbon chains with one H atom on one end and two on the other.     

Electronic absorption spectra of the protonated polyacetylenes HC2nH2+ (n=3,4) in the gas phase

A new approach has been developed for the purpose of measuring the electronic transitions to bound exited states for cations that have been collisionally relaxed to low vibrational and rotational temperatures. This has been used to obtain the first gas phase electronic spectra of the protonated polyacetylenes using a two-color ion-photodissociation approach. Specifically, the origin bands in the B (1)A(1)<-- X(1)A(1) transitions of HC(6)H(2) (+) and HC(8)H(2) (+) (C(2v) geometry) were observed at 26,403.3 and 21,399.8 cm(-1). Data on such cooled systems allow a direct comparison between laboratory and astrophysical measurements.     

Steric effect in the energy transfer reaction of N2 + Rg (3P2) (Rg = Kr, Ar)

Steric effect for the formation of N 2 (B, (3)Pi u ) in the energy transfer reaction of Kr ( (3)P 2) + N 2 has been measured using an oriented Kr ( (3)P 2, M J = 2) beam at a collision energy of 0.07 eV. The N 2 (B, (3)Pi u ) emission intensity was measured as a function of the magnetic orientation field direction in the collision frame. A significant atomic alignment effect on the energy transfer probability was observed. This result was compared with that for the formation of N 2 (C, (3)Pi g ) in the Ar ( (3)P 2) + N 2 reaction. Despite the large difference on the energy transfer cross-section, the atomic alignment dependence for Kr ( (3)P 2) + N 2 is found to be analogous to that for Ar ( (3)P 2) + N 2. It is revealed that the configuration of inner 4p (3p) orbital in the collision frame gives an important role for the stereoselectivity on electron transfer process via the curve-crossing mechanism.     

Structure, energy, and IR spectra of I2*-.nH2O clusters (n=1-8): a theoretical study

The authors report theoretical results on structure, bonding, energy, and infrared spectra of iodine dimer radical anion hydrated clusters, I(2) (-).nH(2)O (n=1-8), based on a systematic study following density functional theory. Several initial guess structures are considered for each size cluster to locate minimum energy conformers with a Gaussian 6-311++G(d,p) split valence basis function (triple split valence 6-311 basis set is applied for iodine). It is observed that three different types of hydrogen bonded structures, namely, symmetrical double hydrogen bonding, single hydrogen bonding, and interwater hydrogen bonding structures, are possible in these hydrated clusters. But conformers having interwater hydrogen bonding arrangements are more stable compared to those of double or single hydrogen bonded structures. It is also noticed that up to four solvent H(2)O units can reside around the solute in interwater hydrogen bonding network. At the maximum six H(2)O units are independently linked to the dimer anion having four double hydrogen bonding and two single hydrogen bonding, suggesting the hydration number of I(2) (-) to be 6. However, conformers having H(2)O units independently linked to the iodine dimer anion are not the most stable structures. In all these hydrated clusters, the odd electron is found to be localized over two I atoms and the two atoms are bound by a three-electron hemi bond. The solvation, interaction, and vertical detachment energies are calculated for all I(2) (-).nH(2)O clusters. Energy of interaction and vertical detachment energy profiles show stepwise saturation, indicating geometrical shell closing in the hydrated clusters, but solvation energy profile fails to show such behavior. A linear correlation is observed between the calculated energy of interaction and vertical detachment energy. It is observed that formation of I(2) (-)-water cluster induces significant shifts from the normal O-H stretching modes of isolated H(2)O. However, bending mode of H(2)O remains insensitive to the successive addition of solvent H(2)O units. Weighted average energy profiles and IR spectra are reported for all the hydrated clusters based on the statistical population of individual conformers at room temperature.     

Infrared spectra of seeded hydrogen clusters: (para-H2)N-N2O and (ortho-H2)N-N2O, N = 2-13

High-resolution infrared spectra of clusters containing para-H2 and/or ortho-H2 and a single nitrous oxide molecule are studied in the 2225-cm(-1) region of the upsilon1 fundamental band of N2O. The clusters are formed in pulsed supersonic jet expansions from a cooled nozzle and probed using a tunable infrared diode laser spectrometer. The simple symmetric rotor-type spectra generally show no resolved K structure, with prominent Q-branch features for ortho-H2 but not para-H2 clusters. The observed vibrational shifts and rotational constants are reported. There is no obvious indication of superfluid effects for para-H2 clusters up to N=13. Sharp transitions due to even larger clusters are observed, but no definite assignments are possible. Mixed (para-H2)N-(ortho-H2)M-N2O cluster line positions can be well predicted by linear interpolation between the corresponding transitions of the pure clusters.     

Carbene-stabilized phosphorus(III)-centered cations [LPX(2)](+) and [L(2)PX](2+) (L = NHC; X = Cl, CN, N(3))

A versatile, high-yielding synthesis of NHC-stabilized [PCl(2)](+) and [PCl](2+) phosphorus synthons has been achieved by using an "onio-substituent transfer" reagent. Subsequent functionalization yields access to cationic cyano- and azido-substituted derivatives which represent first examples of a displacement reaction on NHC-stabilized phosphorus(III)-centered cations. The new salts have been fully characterized by NMR spectroscopy and X-ray crystallography.     

Spectroscopic identification of carbon dioxide clusters: (CO2)6 to (CO2)13

In spite of wide interest in CO(2) clusters, only dimers and trimers have previously been assigned to specific infrared bands. Here, transitions for clusters with 6-13 molecules are identified in the ν(3) region (～2350 cm(-1)). Spectra are observed in a supersonic jet (T ～ 2.5 K) using a tunable laser probe, and analyzed with the aid of cluster calculations based on a widely-used model potential. Vibrational origins show blue-shifts significantly larger than predicted by resonant dipole interactions.     

四齿配体[Ru(iph)(L)2]2+ (L=cpy,mpy, npy)配合物的结构和光谱特征

采用密度泛函的B3LYP和UB3LYP方法分别优化了一系列[Ru(iph)(L)₂]²⁺ (L=cpy (1), mpy (2), npy (3); 其中iph为2,9-双(1′-甲基-2′-咪唑)-1,10-邻二氮杂菲, cpy为4-氰基嘧啶, mpy为4-甲基嘧啶, npy为4-氮二甲基嘧啶)配合物的基态和激发态结构. 利用含时密度泛函理论(TD-DFT)方法, 结合极化连续介质(PCM)模型计算了它们在丙酮溶液中的吸收和发射光谱. 研究结果表明: 优化得到的几何结构参数和相应的实验值符合得非常好. 1和2的最高占据分子轨道主要由金属的d轨道和iph配体的π轨道构成, 但是3主要占据在npy配体上, 而它们的最低空轨道主要由iph配体的π反键轨道占据. 因此, 1和2的最低能吸收和发射属于金属到配体(MLCT)和配体内部(ILCT)的电荷转移跃迁, 而3属于两个配体之间的电荷转移(LLCT)跃迁. 三个配合物的最低能吸收分别在509 nm (1), 527 nm (2)和563 nm (3), 其磷光发射分别在683 nm (1), 852 nm (2)和757 nm (3). 这显示出通过调节L配体的π电子给予能力可以改变最低能吸收和发射的跃迁性质和发光颜色.     

Matrix IR spectra of new organic silanones, (MeO)2Si=O and Ph2Si=O

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2187–2188, September, 1988.     

Hole-burning spectra of phenol-Arn (n = 1, 2) clusters: resolution of the isomer issue

The hole-burning (HB) spectra of phenol-Arn (PhOH-Arn) clusters with n = 1 and 2 have been measured in a molecular beam to clarify the possible existence of isomers. Two species were identified to give rise to signals in the S1-S0 spectrum recorded for the n = 1 cluster; however, one of the species was found to originate from dissociation of an n = 2 cluster. Similarly, three species were observed in the spectrum of the n = 2 cluster, and two of them were assigned to n = 3 and larger clusters. The spectral contamination from larger size clusters was quantitatively explained by the dissociation after photoexcitation. The analysis of the spectra demonstrates that only a single isomer exists in the molecular beam for both the n = 1 and the n = 2 clusters. In addition to two previously detected intermolecular modes, a third low-frequency mode, assigned to an intermolecular bending vibration, is observed for the first time in the HB spectrum of the n = 2 cluster. The assignments of the intermolecular vibrations were confirmed by ab initio MO calculations. The observation of the third intermolecular vibration suggests that the geometry of the n = 2 cluster has Cs or lower symmetry.     

Unusual Anions [LAl(SH)(S)]- and [LAl(S)2]2- stabilized by weakly coordinating imidazolium cations. synthesis of LAl(SSiMe2)2O (L = HC[C(Me)N(Ar)]2, Ar = 2,6-iPr2C6H3)

Deprotonation of an Al-SH moiety has been achieved easily by using N-heterocyclic carbene as the base. Monomeric mono- and bis-imidazolium salts [C(t)H(+)][LAl(SH)(S)](-) ([C(t)H(+)] = N,N'-bis-tert-butylimidazolium), [C(m)H(+)][LAl(SH)(S)](-), and [C(m)H(+)](2)[LAl(S)(2)](2-) ([C(m)H(+)] = N,N'-bismesitylimidazolium), containing unusual anions [LAl(SH)(S)](-) and [LAl(S)(2)](2-), have been synthesized in nearly quantitative yields. Furthermore, [C(m)H(+)](2)[LAl(S)(2)](2-) has been successfully used for the preparation of LAl(SSiMe(2))(2)O containing the [O(Me(2)SiS)(2)](2-) ligand.