A combined ab initio/Franck-Condon study of the A-X single-vibronic-level emission spectrum of CCl2 and the photodetachment spectrum of CCl2 -.

State-of-the-art ab initio calculations have been carried out on the X1A1, ?3B1 and A1B1 states of CCl2 and the X2B1 state of CCl2-. Franck-Condon factors including anharmonicity have been calculated, between the CCl2 states, and between the CCl2- X2B1 state and the CCl2 states. They are used to simulate the A-X single-vibronic-level (SVL) emission spectra of CCl2 determined by M.-L. Lui et al. [PCCP 2003, 5, 352] and the 364 nm laser photodetachment spectrum of CCl2- obtained by R. L. Schwartz et al. [J. Phys. Chem. A 1999, 103, 8213]. Comparison between simulated and observed spectra confirms the vibrational assignments of the X2B1 SVL emission spectra and the T0 position of the A1B1 state of CCl2. For the photodetachment spectrum of CCl2-, spectral simulation shows that the higher binding energy ?3B1(CCl2) <-- X2B1(CCl2-) band is well separated from the X1A1(CCl2) <-- X2B1(CCl2-) band. It is concluded that the observed second band, which overlaps heavily with the X1A1(CCl2) <-- X2B1(CCl2-) band in the photodetachment spectrum of CCl2- cannot be assigned to the CCl2(?3B1) + e --> CCl2-(X2B1) detachment process. Further ab initio calculations carried out in the present investigation support the suggestion that the second band in the 364 nm photodetachment spectrum of CCl2- is due to detachment from an excited state of CCl2-, a linear quartet state, to a triplet state of CCl2. These calculations identify the anionic state to be the lowest 4Sigmag- (4Sigma-) state, which photodetaches vertically to the 3Sigmag- (3Sigma-; adiabatically ?3B1) and/or 3Pi(u) (3Pi) states of CCl2 to give the second band observed in the 364 nm photodetachment spectrum of CCl2-.     

Effects of strong and weak hydrogen bond formation on VCD spectra: a case study of 2-chloropropionic acid

The vibrational circular dichroism (VCD) spectrum of S-(-) and R-(+)-2-chloropropionic acid is thoroughly analyzed. Besides the VCD spectrum of the monomer, the dimers (stabilized by strong hydrogen bonds) and the 2-chloropropionic acid-CHCl(3) complexes (stabilized by a weak hydrogen bond) are studied both experimentally (in solution and in low-temperature Ar matrix) and by quantum chemical computations. It is shown that dimer formation drastically changes, and even weak complex formation can also substantially affect the overall shape of the VCD spectrum. The present and previous results can be generalized for the practice of absolute configuration determination of carboxylic acids by VCD spectroscopy. For these measurements, if bulky groups do not block dimer formation, comparison of the computed spectra of the dimers with the experimental spectra recorded in relatively concentrated (～0.1 mol dm(-3)) solutions is suggested. Our study also shows that due to the stabilization of monomers and/or the formation of weak complexes, the VCD spectrum recorded in CHCl(3) is more complex and, like in the present case, can have a lower intensity than that of the spectrum recorded in CCl(4). Therefore, if solubility allows, CCl(4) is a much preferred solvent over CHCl(3).     

Intermolecular vibrational modes and orientational dynamics of cooperative hydrogen-bonding dimer of 7-azaindole in solution

We observed the low-frequency Raman-active intermolecular vibrational modes of 7-azaindole in CCl(4) by femtosecond Raman-induced Kerr effect spectroscopy. To understand the dynamical aspects and vibrational modes of 7-azaindole in the solution, the ultrafast dynamics of 1-benzofuran in CCl(4) was also examined as a reference and ab initio quantum chemistry calculations were performed for 7-azaindole and 1-benzofuran. The cooperative hydrogen-bonding vibrational bands of 7-azaindole dimer in CCl(4) appeared at 89 cm(-1) and 105 cm(-1) represent the overlap of stagger and wheeling modes and the intermolecular stretching mode, respectively. They are almost independent of the concentration in the solution. We further found from the low-frequency differential Kerr spectra of the solutions with neat CCl(4) that the intermolecular motion in the low frequency region below 20 cm(-1) was less active in the case of 7-azaindole/CCl(4) than in the case of 1-benzofuran/CCl(4). The slow orientational relaxation time in 7-azaindole/CCl(4) is ~3.5 times that in 1-benzofuran/CCl(4) because of the nature of the dimerization of 7-azaindole.     

Ultrafast molecular dynamics of liquid aromatic molecules and the mixtures with CCl4

The ultrafast molecular dynamics of liquid aromatic molecules, benzene, toluene, ethylbenzene, cumene, and 1,3-diphenylpropane, and the mixtures with CCl(4) have been investigated by means of femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The picosecond Kerr transients of benzene, toluene, ethylbenzene, and cumene and the mixtures with CCl(4) show a biexponential feature. 1,3-Diphenylpropane and the mixtures with CCl(4) show triexponential picosecond Kerr transients. The slow relaxation time constants of the aromatic molecules and the mixtures with CCl(4) are qualitatively described by the Stoke-Einstein-Debye hydrodynamic model. The ultrafast dynamics have been discussed based on the Kerr spectra in the frequency range of 0-800 cm(-1) obtained by the Fourier transform analysis of the Kerr transients. The line shapes of the low-frequency intermolecular spectra located at 0-180 cm(-1) frequency range have been analyzed by two Brownian oscillators ( approximately 11 cm(-1) and approximately 45 cm(-1) peaks) and an antisymmetric Gaussian function ( approximately 65 cm(-1) peak). The spectrum shape of 1,3-diphenylpropane is quite different from the spectrum shapes of the other aromatic molecules for the low magnitude of the low-frequency mode of 1,3-diphenylpropane and/or an intramolecular vibration. Although the concentration dependences of the low- and intermediate-frequency intermolecular modes (Brownian oscillators) do not show a significant trend, the width of high-frequency intermolecular mode (antisymmetric Gaussian) becomes narrower with the higher CCl(4) concentration for all the aromatics mixtures with CCl(4). The result indicates that the inhomogeneity of the intermolecular vibrational mode in aromatics/CCl(4) mixtures is decreasing with the lower concentration of aromatics. The intramolecular vibrational modes of the aromatic molecules observed in the Kerr spectra are also shown with the calculation results based on the density functional theory.     

超声射流CCl2自由基激光诱导荧光激发谱

对CCl4/Ar混合气体脉冲直流高压放电产生CCl2自由基,在超声射流冷却下获得了CCl2 1B1－ 1A1420～600 nm 波长范围的激光诱导荧光激发谱,系统标识了9个带系,81个振动带,其中56个振动带是我们新标识的.通过CCl2自由基的超声射流LIF谱与常温下压力为150 Pa 左右的LIF谱相结合分析,初步证实CCl2自由基电子态带源为17 255.04 cm－1.     

First observation of ultrafast intramolecular proton transfer rate between electronic ground states in solution

Despite the importance of ultrafast (time scale exceeding 10(-11) s) intramolecular proton transfer (PT) events between electronic ground states in solution, experimental determination of the rates of such reactions has not yet been accomplished because of the limitations of the utilized methods. The objective of this study was to evaluate the PT rates of intramolecular O···H···O hydrogen-bonded systems in solution through the (1)H spin-lattice relaxation times of the hydroxyl protons, induced by the (1)H-(17)O dipolar interactions (T(1dd)(OH)), taking into account the contribution of the OH reorientational motion to T(1dd)(OH). Solutions of the benzoic acid dimer (BA dimer), 1-benzoyl-6-hydroxy-6-phenylfulvene (Fulvene), and dibenzoylmethane (DBM) were chosen as test systems. For Fulvene in CCl(4), the PT time, τ(PT), was deduced to be 7 × 10(-11) s. In the case of the BA dimer in CCl(4), the τ(PT) value was considerably greater than the OH reorientational correlation time, τ(R(OH)) = 4.3 × 10(-11) s. In contrast, the experimental results for DBM in CCl(4) indicated that the proton is located about midway between the two oxygen atoms, that is, the PT potential energy surface is a single well or a double well with a PT barrier near or below the zero-point energy.     

Ultraviolet absorption and vibrational spectra of 2-fluoro-5-bromopyridine

The ultraviolet absorption spectrum in the range 340-185 nm in the vapour and solution phase has been measured for 2-fluoro-5-bromopyridine. Three fairly intense band systems identified as the pi* <-- pi transitions II, III and IV have been observed. A detailed vibronic analysis of the vapor and solution spectra is presented. The first system of bands is resolved into about sixty-two distinct vibronic bands in the vapour-phase spectrum. The 0,0 band is located at 35944 cm(-1). Two well-developed progressions, in which the excited state frequencies nu'25 (283 cm(-1)) and nu'19 (550 cm(-1)) are excited by several quanta, have been observed. The corresponding excited state vibrational and anharmonicity constants are found to be omega'i = 292 cm(-1), x'ii = 4.5 cm(-1) (i = 25) and omega'i = 563.8 cm(-1), x'ii = 6.9 cm(-1) (i = 19). The other two band systems show no vibronic structure, the band maxima being located at 48346 and 52701 cm(-1), respectively. The oscillator strength of the band systems in different solutions and the excited state dipole moments associated with the first two transitions have been determined by the solvent-shift method. The infrared spectrum in the region 4000-130 cm(-1) and the laser Raman spectrum of the molecule in the liquid state have been measured and a complete vibrational assignment of the observed frequencies is given. A correlation of the ground and excited state fundamental frequencies observed in the UV absorption spectrum with the Raman or infrared frequencies is presented.     

Vibrational dynamics of carboxylic acid dimers in gas and dilute solution

Ultrafast mid-IR transient absorption spectroscopy has been used to study the vibrational dynamics of hydrogen-bonded cyclic dimers of trifluoroacetic acid and formic acid in both the gas and solution phases (0.05 M in CCl(4)). Ultrafast excitation of the broad O-H cyclic dimer band leads, in the gas phase, to large-scale structural changes of the dimer creating a species with a distinct free O-H stretching band on 20 ps and 200 ps timescales. These timescales are assigned to ring-opening and dissociation of the dimer, respectively. In the solution phase, no such structural rearrangement occurs and our results are consistent with previous studies. The gas phase dynamics are insensitive to both the specific excitation energy (over a span of 550 cm(-1)) and the chemical identity of the dimer.     

N-H···π hydrogen-bonding and large-amplitude tipping vibrations in jet-cooled pyrrole-benzene

The N-H···π hydrogen bond is an important intermolecular interaction in many biological systems. We have investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet cooled complex of pyrrole with benzene and benzene-d(6) (Pyr·Bz, Pyr·Bz-d(6)). DFT-D density functional, SCS-MP2 and SCS-CC2 calculations predict a T-shaped and (almost) C(s) symmetric structure with an N-H···π hydrogen bond to the benzene ring. The pyrrole is tipped by ω(S(0)) = ±13° relative to the surface normal of Bz. The N···ring distance is 3.13 ?. In the S(1) excited state, SCS-CC2 calculations predict an increased tipping angle ω(S(1)) = ±21°. The IR depletion spectra support the T-shaped geometry: The NH stretch is redshifted by -59 cm(-1), relative to the "free" NH stretch of pyrrole at 3531 cm(-1), indicating a moderately strong N-H···π interaction. The interaction is weaker than in the (Pyr)(2) dimer, where the NH donor shift is -87 cm(-1) [Dauster et al., Phys. Chem. Chem. Phys., 2008, 10, 2827]. The IR C-H stretch frequencies and intensities of the Bz subunit are very similar to those of the acceptor in the (Bz)(2) dimer, confirming that Bz acts as the acceptor. While the S(1)←S(0) electronic origin of Bz is forbidden and is not observable in the gas-phase, the UV spectrum of Pyr·Bz in the same region exhibits a weak 0 band that is red-shifted by 58 cm(-1) relative to that of Bz (38?086 cm(-1)). The origin appears due to symmetry-breaking of the π-electron system of Bz by the asymmetric pyrrole NH···π hydrogen bond. This contrasts with (Bz)(2), which does not exhibit a 0 band. The Bz moiety in Pyr·Bz exhibits a 6a band at 0 + 518 cm(-1) that is about 20× more intense than the origin band. The symmetry breaking by the NH···π hydrogen bond splits the degeneracy of the ν(6)(e(2g)) vibration, giving rise to 6a' and 6b' sub-bands that are spaced by ～6 cm(-1). Both the 0 and 6 bands of Pyr·Bz carry a progression in the low-frequency (10 cm(-1)) excited-state tipping vibration ω', in agreement with the change of the ω tipping angle predicted by SCS-MP2 and SCS-CC2 calculations.     

Electronic Structure of [Pt(2)(&mgr;-O(2)CCH(3))(4)(H(2)O)(2)](2+) Using the Quasi-Relativistic Xalpha-SW Method: Analysis of Metal-Metal Bonding, Assignment of Electronic Spectra, and Comparison with Rh(2)(&mgr;-O(2)CCH(3))(4)(H(2)O)(2)

The electronic structure and metal-metal bonding in the classic d(7)d(7) tetra-bridged lantern dimer [Pt(2)(O(2)CCH(3))(4)(H(2)O)(2)](2+) has been investigated by performing quasi-relativistic Xalpha-SW molecular orbital calculations on the analogous formate-bridged complex. From the calculations, the highest occupied and lowest unoccupied metal-based levels are delta(Pt(2)) and sigma(Pt(2)), respectively, indicating a metal-metal single bond analogous to the isoelectronic Rh(II) complex. The energetic ordering of the main metal-metal bonding levels is, however, quite different from that found for the Rh(II) complex, and the upper metal-metal bonding and antibonding levels have significantly more ligand character. As found for the related complex [W(2)(O(2)CH)(4)], the inclusion of relativistic effects leads to a further strengthening of the metal-metal sigma bond as a result of the increased involvement of the higher-lying platinum 6s orbital. The low-temperature absorption spectrum of [Pt(2)(O(2)CCH(3))(4)(H(2)O)(2)](2+) is assigned on the basis of Xalpha-SW calculated transition energies and oscillator strengths. Unlike the analogous Rh(II) spectrum, the visible and near-UV absorption spectrum is dominated by charge transfer (CT) transitions. The weak, visible bands at 27 500 and 31 500 cm(-)(1) are assigned to Ow --> sigma(Pt(2)) and OAc --> sigma(Pt(2)) CT transitions, respectively, although the donor orbital in the latter transition has around 25% pi(Pt(2)) character. The intense near-UV band around 37 500 cm(-)(1) displays the typical lower energy shift as the axial substituents are changed from H(2)O to Cl and Br, indicative of significant charge transfer character. From the calculated oscillator strengths, a number of transitions, mostly OAc --> sigma(Pt-O) CT in nature, are predicted to contribute to this band, including the metal-based sigma(Pt(2)) --> sigma(Pt(2)) transition. The close similarity in the absorption spectra of the CH(3)COO(-), SO(4)(2)(-), and HPO(4)(2)(-) bridged Pt(III) complexes suggests that analogous spectral assignments should apply to [Pt(2)(SO(4))(4)(H(2)O)(2)](2)(-) and [Pt(2)(HPO(4))(4)(H(2)O)(2)](2)(-). Consequently, the anomalous MCD spectra reported recently for the intense near-UV band in the SO(4)(2)(-) and HPO(4)(2)(-) bridged Pt(III) complexes can be rationalized on the basis of contributions from either SO(4) --> sigma(Pt-O) or HPO(4) --> sigma(Pt-O) CT transitions. The electronic absorption spectrum of [Rh(2)(O(2)CCH(3))(4)(H(2)O)(2)] has been re-examined on the basis of Xalpha-SW calculated transition energies and oscillator strengths. The intense UV band at approximately 45 000 cm(-)(1) is predicted to arise from several excitations, both metal-centered and CT in origin. The lower energy shoulder at approximately 40 000 cm(-)(1) is largely attributed to the metal-based sigma(Rh(2)) --> sigma(Rh(2)) transition.     

Near-infrared spectroscopy of ethylene and ethylene dimer in superfluid helium droplets

The nu(5)+nu(9) spectra of ethylene, C(2)H(4), and its dimer, solvated in helium nanodroplets, have been recorded in the wavelength region near 1.6 microm. The monomer transitions show homogeneous broadening of approximately 0.5 cm(-1), which is interpreted as due to an upper state vibrational relaxation lifetime of approximately 10 ps. Nearly resonant vibrational energy transfer (nu(5)+nu(9)-->2nu(5)) is proposed as the relaxation pathway. The dimer gives a single unresolved absorption feature located 4 cm(-1) to the red of the monomer band origin. The scaling of moments of inertia upon solvation in helium is 1.18 for the monomer and >2.5 for the dimer. In terms of the adiabatic following approximation, this classifies the monomer as a fast rotor and the dimer as a slow rotor.     

13C NMR, infrared, solvation and theoretical investigation of the conformational isomerism in 1-haloacetones (X = Cl, Br and I)

The solvent dependence of the 13C NMR spectra of chloroacetone (CA), bromoacetone (BA) and iodoacetone (IA) are reported and the 3J(CH) couplings analysed using ab initio calculations and solvation theory. In CA the energy difference (E(cis) - E(gauche)) between the cis (Cl-C-C=O 0 degrees) and gauche (Cl-C-C=O 155 degrees) conformers is 1.7 kcal mol(-1) in the vapour, decreasing to 0.8 kcal mol(-1) in CCl4 solution and to -1.0 kcal mol(-1) in the pure liquid. The conformational equilibrium, in BA, is between the more polar cis (Br-C-C=O 0 degrees) and gauche (Br-C-C=O 132 degrees) conformations. The energy difference (E(cis) - E(gauche)) is 1.8 kcal mol(-1) in the vapour, decreasing to 0.9 kcal mol(-1) in CCl4 solution and to -0.4 kcal mol(-1) in the pure liquid. The energy difference (E(cis) - E(gauche)), in IA, between the cis (I-C-C=O 0 degrees) and gauche (I-C-C=O 104 degrees) conformers is 1.1 kcal mol(-1) in the vapour phase, decreasing to 0.5 kcal mol(-1) in CCl4 solution and to -0.5 kcal mol(-1) in the pure liquid. The vapour state energy difference for BA [1.4 kcal mol(-1) at B3LYP/6-311++G(d,p)] and for IA [1.6 kcal mol(-1) at B3LYP/6-311++G(d,p)/LANL2DZ)] are in very good agreement with the above values. For CA the agreement is also satisfactory [1.4 kcal mol(-1) at B3LYP/6-311++G(d,p)].     

Measurement and revised analysis of the torsional combination band of the nonpolar N2O dimer at 2249 cm(-1)

The high-resolution infrared spectrum of the weakly-bound dimer (N(2)O)(2) is studied using a rapid-scan tunable-diode laser spectrometer to probe a pulsed supersonic jet expansion. An observed band with c-type rotational structure is assigned as a combination of the intramolecular N(2)O nu(1) stretching vibration and the intermolecular out-of-plane dimer torsional vibration, with a vibrational origin at 2249.360 cm(-1). The resulting torsional frequency for the nonpolar N(2)O dimer is about 21.5 cm(-1). The present rotational analysis is completely different from that reported previously for the same band [Hecker et al., Phys. Chem. Chem. Phys., 2003, 5, 2333], which gave a band origin some 1.53 cm(-1) lower.     

The vibrational spectrum of the stable free radical 1,1,3,3-tetramethylisoindolin-2-yloxyl

Solid and solution IR and Raman spectra of a stable nitroxide radical, 1,1,3,3-tetramethylisoindolin-2-yloxyl (TMIO), are reported and compared to ab initio density functional theory calculations of the vibrational frequencies to obtain unequivocal band assignments, in particular of the NO stretching frequency, nu(NO). The band position was found to be at 1431 cm(-1) for the solid, which is well outside the previously published range of 1310-1380 cm(-1) for nitroxide radicals. This apparently anomalous peak position was confirmed by undertaking isotopic substitution studies through the preparation and recording of vibrational spectra of tetrakis(trideuteriomethyl)isoindolin-2-yloxyl ([2H12]-TMIO) and [2H12,15N]-TMIO analogues. Solution spectra of TMIO in methanol and CCl4 are assessed for possible solvent-dependent spin density distribution effects in the NO bond.     

Infrared spectra of ethylene clusters: (C2D4)2 and (C2D4)3

Spectra of ethylene dimers and trimers are studied in the ν(11) fundamental band region of C(2)D(4) (≈2200 cm(-1)) using a tuneable quantum cascade laser to probe a pulsed supersonic slit jet expansion. The dimer spectrum is that of a prolate symmetric top perpendicular band, with a distinctive appearance because the A rotational constant is almost exactly equal to six times the B constant. The analysis supports the previously determined cross-shaped dimer structure with D(2d) symmetry. An ethylene trimer has not previously been observed with rotational resolution. The spectrum is that of an oblate symmetric top parallel band. It leads to a proposed trimer structure which is barrel shaped and has C(3h) or C(3) symmetry, with the ethylene monomer C-C axes approximately aligned along the trimer symmetry axis.     

Spectroscopic characterization of chromite from the Moa-Baracoa Ophiolitic Massif, Cuba

The Cuban chromites with a spinel structure, FeCr2O4 have been studied using optical absorption and EPR spectroscopy. The spectral features in the electronic spectra are used to map the octahedral and tetrahedral co-ordinated cations. Bands due Cr3+ and Fe3+ ions could be distinguished from UV-vis spectrum. Chromite spectrum shows two spin allowed bands at 17,390 and 23,810 cm(-1) due to Cr3+ in octahedral field and they are assigned to 4A2g(F) --> 4T2g(F) and 4A2g(F) --> 4T1g(F) transitions. This is in conformity with the broad resonance of Cr3+ observed from EPR spectrum at g = 1.903 and a weak signal at g = 3.861 confirms Fe3+ impurity in the mineral. Bands of Fe3+ ion in the optical spectrum at 13,700, 18,870 and 28,570 cm(-1) are attributed to 6A1g(S) --> 4T1g(G), 6A1g(S) --> 4T2g(G) and 6A1g(S) --> 4T2g(P) transitions, respectively. Near-IR reflectance spectroscopy has been used effectively to show intense absorption bands caused by electronic spin allowed d-d transitions of Fe2+ in tetrahedral symmetry, in the region 5000-4000 cm(-1). The high frequency region (7500-6500 cm(-1)) is attributed to the overtones of hydroxyl stretching modes. Correlation between Raman spectral features and mineral chemistry are used to interpret the Raman data. The Raman spectrum of chromite shows three bands in the CrO stretching region at 730, 560 and 445 cm(-1). The most intense peak at 730 cm(-1) is identified as symmetric stretching vibrational mode, A1g(nu1) and the other two minor peaks at 560 and 445 cm(-1) are assigned to F2g(nu4) and E(g)(nu2) modes, respectively. Cation substitution in chromite results various changes both in Raman and IR spectra. In the low-wavenumber region of Raman spectrum a significant band at 250 cm(-1) with a component at 218 cm(-1) is attributed F2g(nu3) mode. The minor peaks at 195, 175, 160 cm(-1) might be due to E(g) and F2g symmetries. Broadening of the peak of A1g mode and shifting of the peak to higher wavenumber observed as a result of increasing the proportion of Al3+O6. The presence of water in the mineral shows bands in the IR spectrum at 3550, 3425, 3295, 1630 and 1455 cm(-1). The vibrational spectrum of chromite gives raise to four frequencies at 985, 770, 710 and 650 cm(-1). The first two frequencies nu1 and nu2 are related to the lattice vibrations of octahedral groups. Due to the influence of tetrahedral bivalent cation, vibrational interactions occur between nu3 and nu4 and hence the low frequency bands, nu3 and nu4 correspond to complex vibrations involving both octahedral and tetrahedral cations simultaneously. Cr3+ in Cuban natural chromites has highest CFSE (20,868 cm(-1)) when compared to other oxide minerals.     

High-resolution threshold photoelectron study of the propargyl radical by the vacuum ultraviolet laser velocity-map imaging method

By employing the vacuum ultraviolet (VUV) laser velocity-map imaging (VMI) photoelectron scheme to discriminate energetic photoelectrons, we have measured the VUV-VMI-threshold photoelectrons (VUV-VMI-TPE) spectra of propargyl radical [C(3)H(3)(X?(2)B(1))] near its ionization threshold at photoelectron energy bandwidths of 3 and 7 cm(-1) (full-width at half-maximum, FWHM). The simulation of the VUV-VMI-TPE spectra thus obtained, along with the Stark shift correction, has allowed the determination of a precise value 70 156 ± 4 cm(-1) (8.6982 ± 0.0005 eV) for the ionization energy (IE) of C(3)H(3). In the present VMI-TPE experiment, the Stark shift correction is determined by comparing the VUV-VMI-TPE and VUV laser pulsed field ionization-photoelectron (VUV-PFI-PE) spectra for the origin band of the photoelectron spectrum of the X?(+)-X? transition of chlorobenzene. The fact that the FWHMs for this origin band observed using the VUV-VMI-TPE and VUV-PFI-PE methods are nearly the same indicates that the energy resolutions achieved in the VUV-VMI-TPE and VUV-PFI-PE measurements are comparable. The IE(C(3)H(3)) value obtained based on the VUV-VMI-TPE measurement is consistent with the value determined by the VUV laser PIE spectrum of supersonically cooled C(3)H(3)(X?(2)B(1)) radicals, which is also reported in this article.     

FTIR studies of plasticized poly(vinyl alcohol)-chitosan blend doped with NH4NO3 polymer electrolyte membrane

Fourier transform infrared (FTIR) spectroscopy studies of poly(vinyl alcohol) (PVA), and chitosan polymer blend doped with ammonium nitrate (NH(4)NO(3)) salt and plasticized with ethylene carbonate (EC) have been performed with emphasis on the shift of the carboxamide, amine and hydroxyl bands. 1% acetic acid solution was used as the solvent. It is observed from the chitosan film spectrum that evidence of polymer-solvent interaction can be observed from the shifting of the carboxamide band at 1660 cm(-1) and the amine band at 1591 cm(-1) to 1650 and 1557 cm(-1) respectively and the shift of the hydroxyl band from 3377 to 3354 cm(-1). The hydroxyl band in the spectrum of PVA powder is observed at 3354 cm(-1) and is observed at 3343 cm(-1) in the spectrum of the PVA film. On addition of NH(4)NO(3) up to 30 wt.%, the carboxamide, amine and hydroxyl bands shifted from 1650, 1557 and 3354 cm(-1) to 1642, 1541 and 3348 cm(-1) indicating that the chitosan has complexed with the salt. In the PVA-NH(4)NO(3) spectrum, the hydroxyl band has shifted from 3343 to 3272 cm(-1) on addition of salt from 10 to 30 wt.%. EC acts as a plasticizing agent since there is no shift in the bands as observed in the spectrum of PVA-chitosan-EC films. The mechanism of ion migration is proposed for the plasticized and unplasticized PVA-chitosan-NH(4)NO(3) systems. In the spectrum of PVA-chitosan-NH(4)NO(3)-EC complex, the doublet CO stretching in EC is observed in the vicinity 1800 and 1700. This indicates that there is some interaction between the salt and EC.     

IR plus vacuum ultraviolet spectroscopy of neutral and ionic organic acid molecules and clusters: acetic acid

Infrared (IR) vibrational spectroscopy of acetic acid (A) neutral and ionic monomers and clusters, employing vacuum ultraviolet (VUV), 10.5 eV single photon ionization of supersonically expanded and cooled acetic acid samples, is presented and discussed. Molecular and cluster species are identified by time of flight mass spectroscopy: the major mass features observed are A(n)H(+) (n=1-9), ACOOH(+) (VUV ionization) without IR radiation present, and A(+) with both IR and VUV radiation present. The intense feature ACOOH(+) arises from the cleavage of (A)(2) at the beta-CC bond to generate ACOOH(+)+CH(3) following ionization. The vibrational spectrum of monomeric acetic acid (2500-7500 cm(-1)) is measured by nonresonant ionization detected infrared (NRID-IR) spectroscopy. The fundamentals and overtones of the CH and OH stretches and some combination bands are identified in the spectrum. Mass selected IR spectra of neutral and cationic acetic acid clusters are measured in the 2500-3800 cm(-1) range employing nonresonant ionization dip-IR and IR photodissociation (IRPD) spectroscopies, respectively. Characteristic bands observed at approximately 2500-2900 cm(-1) for the cyclic ring dimer are identified and tentatively assigned. For large neutral acetic acid clusters A(n)(n>2), spectra display only hydrogen bonded OH stretch features, while the CH modes (2500-2900 cm(-1)) do not change with cluster size n. The IRPD spectra of protonated (cationic) acetic acid clusters A(n)H(+) (n=1-7) exhibit a blueshift of the free OH stretch with increasing n. These bands finally disappear for n> or =6, and one broad and weak band due to hydrogen bonded OH stretch vibrations at approximately 3350 cm(-1) is detected. These results indicate that at least one OH group is not involved in the hydrogen bonding network for the smaller (n< or =5) A(n)H(+) species. The disappearance of the free OH stretch feature at n> or =6 suggests that closed cyclic structures form for A(n)H(+) for the larger clusters (n> or =6).     

Effects of torsion on O-H stretch overtone spectra and direct overtone photolysis of methyl hydroperoxide

We use laser photoacoustic spectroscopy to obtain overtone spectra at three through six quanta of O-H stretch excitation (3nu(OH)-6nu(OH)) for methyl hydroperoxide (MeOOH). Extending the spectral regions beyond our previous work reveals new features that can be attributed to transitions involving torsion about the O-O bond. Experimental spectral profiles (3nu(OH)-6nu(OH)) and cross sections (3nu(OH)-5nu(OH)) at room temperature show a good agreement with the simulated spectra that we obtain from ab initio calculations employing a vibration-torsion model at 298 K. A Birge-Sponer analysis yields experimental values for the O-H stretch frequency (omega=3773+/-15 cm(-1)) and anharmonicity (omegax=94+/-3 cm(-1)). We also detect OH radicals by laser-induced fluorescence and present photodissociation action spectra of MeOOH in the regions of 4nu(OH) and 5nu(OH). While the spectral profile at 5nu(OH) mimics the photoacoustic spectrum, the peak intensity for transitions to torsionally excited states is relatively more intense in the action spectrum at 4nu(OH), reflecting the fact that the 4nu(OH) excitation energy is below the literature dissociation energy (D0=42.6+/-1 kcal mol(-1)) so that features in the action spectrum come from thermally populated excited states. Finally, we use our calculations to assign contributions to individual peaks in the room-temperature spectra and relate our findings to a recent dynamics study in the literature.