Far-infrared absorption of water clusters by first-principles molecular dynamics

Based on first-principle molecular dynamic simulations, we calculate the far-infrared spectra of small water clusters (H(2)O)(n) (n = 2, 4, 6) at frequencies below 1000 cm(-1) and at 80 K and at atmospheric temperature (T>200 K). We find that cluster size and temperature affect the spectra significantly. The effect of the cluster size is similar to the one reported for confined water. Temperature changes not only the shape of the spectra but also the total strength of the absorption, a consequence of the complete anharmonic nature of the classical dynamics at high temperature. In particular, we find that in the frequency region up to 320 cm(-1), the absorption strength per molecule of the water dimer at 220 K is significantly larger than that of bulk liquid water, while tetramer and hexamer show bulklike strengths. However, the absorption strength of the dimer throughout the far-infrared region is too small to explain the measured vapor absorption continuum, which must therefore be dominated by other mechanisms.     

Water dimer proton affinity from the kinetic method: dissociation energy of the water dimer

The proton affinity of water dimer was measured, using the kinetic method with nitrile reference bases, to be 808 +/- 6 kJ mol(-1). The difference between the measured value and the proton affinity of a single water molecule (690 +/- 4 kJ mol(-1)) reflects the difference in solvation energy for two neutral water molecules (the hydrogen bond energy of water dimer), and the energy for solvation of hydronium cation and water. Using the measured proton affinity of the dimer along with ancillary data yields an experimental value of the hydrogen bond energy of neutral water dimer, 18 +/- 9 kJ mol(-1), in good agreement with previous experimental and theoretical values. The proton affinity of the dimer measured by using alcohol references is ca 100 kJ mol(-1) too low, likely because the structure of the protonated cluster is not well-suited for kinetic method measurements. These results highlight the importance of choosing reference bases that form cluster ions consisting of a proton bound complex between the water dimer and the reference base.     

Contribution of water dimer absorption to the millimeter and far infrared atmospheric water continuum

We present a rigorous calculation of the contribution of water dimers to the absorption coefficient alpha(nu,T) in the millimeter and far infrared domains, over a wide range (276-310 K) of temperatures. This calculation relies on the explicit consideration of all possible transitions within the entire rovibrational bound state manifold of the dimer. The water dimer is described by the flexible 12-dimensional potential energy surface previously fitted to far IR transitions [C. Leforestier et al., J. Chem. Phys. 117, 8710 (2002)], and which was recently further validated by the good agreement obtained for the calculated equilibrium constant Kp(T) with experimental data [Y. Scribano et al., J. Phys. Chem. A. 110, 5411 (2006)]. Transition dipole matrix elements were computed between all rovibrational states up to an excitation energy of 750 cm(-1), and J=K=5 rotational quantum numbers. It was shown by explicit calculations that these matrix elements could be extrapolated to much higher J values (J=30). Transitions to vibrational states located higher in energy were obtained from interpolation of computed matrix elements between a set of initial states spanning the 0-750 cm(-1) range and all vibrational states up to the dissociation limit (approximately 1200 cm(-1)). We compare our calculations with available experimental measurements of the water continuum absorption in the considered range. It appears that water dimers account for an important fraction of the observed continuum absorption in the millimeter region (0-10 cm(-1)). As frequency increases, their relative contribution decreases, becoming small (approximately 3%) at the highest frequency considered nu=944 cm(-1).     

Communication: determination of the bond dissociation energy (D0) of the water dimer, (H2O)2, by velocity map imaging

The bond dissociation energy (D(0)) of the water dimer is determined by using state-to-state vibrational predissociation measurements following excitation of the bound OH stretch fundamental of the donor unit of the dimer. Velocity map imaging and resonance-enhanced multiphoton ionization (REMPI) are used to determine pair-correlated product velocity and translational energy distributions. H(2)O fragments are detected in the ground vibrational (000) and the first excited bending (010) states by 2 + 1 REMPI via the C? (1)B(1) (000) ← X? (1)A(1) (000 and 010) transitions. The fragments' velocity and center-of-mass translational energy distributions are determined from images of selected rovibrational levels of H(2)O. An accurate value for D(0) is obtained by fitting both the structure in the images and the maximum velocity of the fragments. This value, D(0) = 1105 ± 10 cm(-1) (13.2 ± 0.12 kJ/mol), is in excellent agreement with the recent theoretical value of D(0) = 1103 ± 4 cm(-1) (13.2 ± 0.05 kJ∕mol) suggested as a benchmark by Shank et al. [J. Chem. Phys. 130, 144314 (2009)].     

Composition and thermochemistry of silver bromide vapor

The mole fractions of AgBr and Ag3Br3 in the saturated vapor at 840 K have been evaluated from the vapor mass spectrum, by comparison with the corresponding spectrum of AgCl vapor, where the monomer/trimer ratio is known accurately from vapor molecular weight measurements. Combination of these results with new measurements of the vapor pressure of molten AgBr by the torsion-effusion method in the range 805-936 K yielded the third law enthalpies of vaporization and the standard enthalpies of formation DeltafH degrees 298(AgBr, g) = 27.8 +/- 0.3 kcal mol(-1) and DeltafH degrees 298(Ag3Br3, g) = -19.0 +/- 1 kcal mol(-1). The dissociation energy, D degrees 0(AgBr), is found to be 66.4 +/- 0.3 kcal mol(-1), or 2.88 +/- 0.01 eV, some 3.5-5 kcal mol(-1) lower than previous literature values. Approximate thermochemical stabilities of the dimer species Ag2Cl2 and Ag2Br2 have also been evaluated.     

Studies of the kinetics and thermochemistry of the forward and reverse reaction Cl + C6H6 = HCl + C6H5

The laser flash photolysis resonance fluorescence technique was used to monitor atomic Cl kinetics. Loss of Cl following photolysis of CCl4 and NaCl was used to determine k(Cl + C6H6) = 6.4 x 10(-12) exp(-18.1 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 578-922 K and k(Cl + C6D6) = 6.2 x 10(-12) exp(-22.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 635-922 K. Inclusion of literature data at room temperature leads to a recommendation of k(Cl + C6H6) = 6.1 x 10(-11) exp(-31.6 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) for 296-922 K. Monitoring growth of Cl during the reaction of phenyl with HCl led to k(C6H5 + HCl) = 1.14 x 10(-12) exp(+5.2 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 294-748 K, k(C6H5 + DCl) = 7.7 x 10(-13) exp(+4.9 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 292-546 K, an approximate k(C6H5 + C6H5I) = 2 x 10(-11) cm(3) molecule(-1) s(-1) over 300-750 K, and an upper limit k(Cl + C6H5I) < or = 5.3 x 10(-12) exp(+2.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 300-750 K. Confidence limits are discussed in the text. Third-law analysis of the equilibrium constant yields the bond dissociation enthalpy D(298)(C6H5-H) = 472.1 +/- 2.5 kJ mol(-1) and thus the enthalpy of formation Delta(f)H(298)(C6H5) = 337.0 +/- 2.5 kJ mol(-1).     

Ab initio potential energy and dipole moment surfaces of (H2O)2

A full-dimensional ab initio potential energy surface (PES) and dipole moment surface (DMS) are reported for the water dimer, (H2O)2. The CCSD(T)-PES is a very precise fit to 19,805 ab initio energies obtained with the coupled-cluster (CCSD(T)) method, using an aug-cc-pVTZ basis. The standard counterpoise correction was applied to approximately eliminate basis set superposition errors. The fit is based on an approach that incorporates the permutational symmetry of identical atoms [Huang, X.; Braams, B.; Bowman, J. M. J. Chem.Phys. 2005, 122, 044308]. The DMS is a fit to the dipole moment obtained with M?ller-Plesset (MP2) theory, using an aug-cc-pVTZ basis. The PES has an RMS fitting error of 31 cm(-1) for energies below 20,000 cm(-1), relative to the global minimum. This surface can describe various internal floppy motions, including various monomer inversions, and isomerization pathways. Ten characteristic stationary points have been located on the surface, four of which are transition structures and the rest are higher order saddle points. Their geometrical and vibrational properties are presented and compared with available previous theoretical work. The CCSD(T)-PES and MP2-DMS dissociate correctly (and symmetrically) to two H2O monomers, with D(e) = 1665.7 cm(-1) (19.93 kJ/mol). Accurate quantum calculations of the zero-point energy of the dimer (using diffusion Monte Carlo) and the monomers (using a vibrational configuration interaction approach) are reported, and these together with D(e) give a value of D0 of 1042 cm(-1) (12.44 kJ/mol). A best estimated value is 1130 cm(-1) (13.5 kJ/mol).     

Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water dimer. II. Infrared spectrum and vibrational dynamics

The infrared absorption spectrum of the protonated water dimer (H5O2+) is simulated in full dimensionality (15 dimensional) in the spectral range of 0-4000 cm(-1). The calculations are performed using the multiconfiguration time-dependent Hartree (MCTDH) method for propagation of wavepackets. All the fundamentals and several overtones of the vibrational motion are computed. The spectrum of H5O2+ is shaped to a large extent by couplings of the proton-transfer motion to large amplitude fluxional motions of the water molecules, water bending and water-water stretch motions. These couplings are identified and discussed, and the corresponding spectral lines are assigned. The large couplings featured by H5O2+ do not hinder, however, to describe the coupled vibrational motion by well defined simple types of vibration (stretching, bending; etc.) based on well defined modes of vibration, in terms of which the spectral lines are assigned. Comparison of our results to recent experiments and calculations on the system is given. The reported MCTDH IR spectrum is in very good agreement to the recently measured spectrum by Hammer et al. [J. Chem. Phys. 122, 244301 (2005)].     

Kinetics of Water Exchange on the Dihydroxo-Bridged Rhodium(III) Hydrolytic Dimer

()()Conventional (18)O isotopic labeling techniques have been used to measure the water exchange rates on the Rh(III) hydrolytic dimer [(H(2)O)(4)Rh(&mgr;-OH)(2)Rh(H(2)O)(4)](4+) at I = 1.0 M for 0.08 < [H(+)] < 0.8 M and temperatures between 308.1 and 323.1 K. Two distinct pathways of water exchange into the bulk solvent were observed (k(fast) and k(slow)) which are proposed to correspond to exchange of coordinated water at positions cis and trans to bridging hydroxide groups. This proposal is supported by (17)O NMR measurements which clearly showed that the two types of water ligands exchange at different rates and that the rates of exchange matched those from the (18)O labeling data. No evidence was found for the exchange of label in the bridging OH groups in either experiment. This contrasts with findings for the Cr(III) dimer. The dependence of both k(fast) and k(slow) on [H(+)] satisfied the expression k(obs) = (k(O)[H(+)](tot) +k(OH)K(a1))/([H(+)](tot) + K(a1)) which allows for the involvement of fully protonated and monodeprotonated Rh(III) dimer. The following rates and activation parameters were determined at 298 K. (i) For fully protonated dimer: k(fast) = 1.26 x 10(-)(6) s(-)(1) (DeltaH() = 119 +/- 4 kJ mol(-)(1) and DeltaS() = 41 +/- 12 J K(-)(1) mol(-)(1)) and k(slow) = 4.86 x 10(-)(7) s(-)(1) (DeltaH() = 64 +/- 9 kJ mol(-)(1) and DeltaS() = -150 +/- 30 J K(-)(1) mol(-)(1)). (ii) For monodeprotonated dimer: k(fast) = 3.44 x 10(-)(6) s(-)(1) (DeltaH() = 146 +/- 4 kJ mol(-)(1) and DeltaS() = 140 +/- 11 J K(-)(1) mol(-)(1)) and k(slow) = 2.68 x 10(-)(6) s(-)(1) (DeltaH() = 102 +/- 3 kJ mol(-)(1) and DeltaS() = -9 +/- 11 J K(-)(1) mol(-)(1)). Deprotonation of the Rh(III) dimer was found to labilize the primary coordination sphere of the metal ions and thus increase the rate of water exchange at positions cis and trans to bridging hydroxides but not to the same extent as for the Cr(III) dimer. Activation parameters and mechanisms for ligand substitution processes on the Rh(III) dimer are discussed and compared to those for other trivalent metal ions and in particular the Cr(III) dimer.     

Theory of the photodissociation of ozone in the Hartley continuum; effect of vibrational excitation and O(1D) atom velocity distribution

The effect of vibrational excitation on the photodissociation cross section of ozone in the Hartley continuum is examined. The calculations make use of newly computed potential energy and transition dipole moment surfaces. The initial vibrational states of the ozone are computed using grid based techniques and the first few ab initio computed vibrational energy level spacings agree to within 10 cm(-1) with experimental values. The computed total absorption cross sections arising from different initial vibrational states of ozone are discussed in the light of the nature of the transition dipole moment surface. The computed cross section for excitation from the ground vibrational-rotational state is in good agreement with the experimentally measured cross section. Excitation of the asymmetric stretching vibration of ozone has a marked effect on both the form and magnitude of the photodissociation cross section. The velocity distributions of highly reactive O(1D) atoms arising from the photodissociation process in different wavelength ranges is also presented. The results show that the O(1D) atoms travel with a most probable translational velocity of 2.030 km s(-1) corresponding to a translational energy of 0.342 eV or 33.0 kJ mol(-1).     

Quantum Monte Carlo calculations of the dissociation energy of the water dimer

We report diffusion quantum Monte Carlo (DMC) calculations of the equilibrium dissociation energy D(e) of the water dimer. The dissociation energy measured experimentally, D(0), can be estimated from D(e) by adding a correction for vibrational effects. Using the measured dissociation energy and the modern value of the vibrational energy Mas et al., [J. Chem. Phys. 113, 6687 (2000)] leads to D(e)=5.00+/-0.7 kcal mol(-1), although the result Curtiss et al., [J. Chem. Phys. 71, 2703 (1979)] D(e)=5.44+/-0.7 kcal mol(-1), which uses an earlier estimate of the vibrational energy, has been widely quoted. High-level coupled cluster calculations Klopper et al., [Phys. Chem. Chem. Phys. 2, 2227 (2000)] have yielded D(e)=5.02+/-0.05 kcal mol(-1). In an attempt to shed new light on this old problem, we have performed all-electron DMC calculations on the water monomer and dimer using Slater-Jastrow wave functions with both Hartree-Fock approximation (HF) and B3LYP density functional theory single-particle orbitals. We obtain equilibrium dissociation energies for the dimer of 5.02+/-0.18 kcal mol(-1) (HF orbitals) and 5.21+/-0.18 kcal mol(-1) (B3LYP orbitals), in good agreement with the coupled cluster results.     

NC-(CF2)4-CNSSN radical containing 1,2,3,5-dithiadiazolyl radical dimer exhibiting triplet excited states at low temperature and thermal hysteresis on melting-solidification: structural, spectroscopic, and magnetic characterization

A high yield, one-pot synthesis of the 1,2,3,5-dithiadiazolyl radical NC-(CF2)4-CNSSN radical by reduction of the corresponding 1,3,2,4-dithiadiazolium salt is reported. In the solid state, the title compound is dimerized in trans-cofacial fashion with intra-dimeric Sdelta+...N(delta-) interactions of ca. 3.2 angstroms, and the dimeric units are linked by electrostatic -C triple bond N(delta-)...Sdelta+ interactions forming an infinite chain. Magnetic susceptibility measurements performed on the solid state sample indicate a magnetic moment of 1.8 microB per dimer (1.3 microB per monomer) at 300 K and a good fit to the Bleaney-Bowers model in the temperature range 2-300 K with 2J = -1500 +/- 50 cm(-1), g = 2.02(5), rho = 0.90(3)%, and TIP = 1.25(4) x 10(-3) emu mol(-1). The [NC-(CF2)4-CNSSN radical]2 dimer is the second example of a 1,2,3,5-dithiadiazolyl radical dimer with an experimentally detected triplet excited state as probed by solid-state EPR [2J = -1730 +/- 100 cm(-1), |D| = 0.0278(5) cm(-1), |E| = 0.0047(5) cm(-1)]. The value of the singlet-triplet gap has enabled us to estimate the "in situ" dimerization energy of the radical dimer as ca. -10 kJ mol(-1). The diradical character of the dimer was calculated [CASSCF(6,6)/6-31G*] as 35%. The title radical shows magnetic bistability in the temperature range of 305-335 K as probed by the solid-state EPR presumably arising from the presence of a metastable paramagnetic supercooled phase. Bistability is accompanied by thermochromic behavior with a color change from dark green (dimeric solid) to dark brown (paramagnetic liquid).     

Factors influencing Al(3+)-dimer speciation and stability from density functional theory calculations

We have investigated aqueous Al-dimer complexes using density functional theory methods (e.g. the B3LYP exchange-correlation functional and the 6-311++G(d,p) basis set). In these calculations interactions between the Al(3+) cations and the H(2)O or OH(-) coordinating ligands are considered explicitly while the second hydration shell and remaining solvent are treated as a continuum under the IEF-PCM formalism. The Al-dimer chemical reactivity is discussed by analysis of changes in geometry, electronic structure and Gibbs free energy of formation, relative to two independent Al(H(2)O) monomers, as a function of water and hydroxide coordination. Our results indicate that the mechanism of cooperativity, i.e. decreased Al-water bond stability with increasing OH(-) coordination and increased water ligand hydrolysis as complex CN decreases, is operating on the dimer species and that, therefore, a wide variety of dimer species are available. While the stability of these species is observed to be dependent on the number of water and hydroxide ligands, the hydroxide bridging structure (singly, doubly and triply bridged species are considered) does not appear to correlate with dimer stability. Interestingly, intra-molecular H-bonds (in the form of the well known H(3)O bridge as well as two bridging structures, H(4)O(2) and H(2)O, that have not, to our knowledge, been previously considered) are observed to influence dimer stability. The evaluation of the equilibrium mole fraction of the dimer species in equilibrium with the aqueous Al(3+) monomer species of our previous study displays the qualitatively correct trend of solution composition as pH increases, namely monomeric aqueous Al(3+) and Al(OH) complexes dominate at low and high pH, respectively, and all remaining monomer and dimer species exist at intermediate pH. Further refinement of our data set by eliminating dimer complexes with OH/Al ratios greater than 2.6 brings our predicted equilibrium mole fraction distributions into excellent agreement with experimental observations. The triply bridged dimer is observed in low amounts while the singly and doubly bridged dimers dominate our model system at pH = ～4-7.     

Kinetic and product study of the gas-phase reactions of OH radicals, NO(3) radicals, and O(3) with (C(2)H(5)O)(2)P(S)CH(3) and (C(2)H(5)O)(3)PS

Rate constants for the reactions of OH radicals and NO3 radicals with O,O-diethyl methylphosphonothioate [(C(2)H(5)O)(2)P(S)CH(3); DEMPT] and O,O,O-triethyl phosphorothioate [(C(2)H(5)O)(3)PS; TEPT] have been measured using relative rate methods at atmospheric pressure of air over the temperature range 296-348 K for the OH radical reactions and at 296 +/- 2 K for the NO(3) radical reactions. At 296 +/- 2 K, the rate constants obtained for the OH radical reactions (in units of 10(-11) cm(3) molecule(-1) s(-1)) were 20.4 +/- 0.8 and 7.92 +/- 0.27 for DEMPT and TEPT, respectively, and those for the NO(3) radical reactions (in units of 10(-15) cm(3) molecule(-1) s(-1)) were 2.01 +/- 0.20 and 1.03 +/- 0.10, respectively. Upper limits to the rate constants for the reactions of O(3) with DEMPT and TEPT of <6 x 10(-20) cm(3) molecule(-1) s(-1) were determined in each case. Rate constants for the OH radical reactions, measured relative to k(OH + alpha-pinene) = 1.21 x 10(-11) e(436/T) cm(3) molecule(-1) s(-1), resulted in the Arrhenius expressions k(OH + DEMPT) = 1.08 x 10(-11) e(871+/-25)/T cm(3) molecule(-1) s(-1) and k(OH + TEPT) = 8.21 x 10(-13) e(1353+/-49)/T cm(3) molecule(-1) s(-1) over the temperature range 296-348 K, where the indicated errors are two least-squares standard deviations and do not include the uncertainties in the reference rate constant. Diethyl methylphosphonate was identified and quantified from the OH radical and NO(3) radical reactions with DEMPT, with formation yields of 21 +/- 4%, independent of temperature, from the OH radical reaction and 62 +/- 11% from the NO(3) radical reaction at 296 +/- 2 K. Similarly, triethyl phosphate was identified and quantified from the OH radical and NO(3) radical reactions with TEPT, with formation yields of 56 +/- 9%, independent of temperature, from the OH radical reaction and 78 +/- 15% from the NO(3) radical reaction at 296 +/- 2 K.     

Photophysical properties of ricin

The molar absorption coefficient of ricin in phosphate-buffered saline (PBS) at 279 nm was measured as (93,900+/-3300) L mol(-1) cm(-1). The concentration of ricin was determined using amino acid analysis. The absorption spectrum of ricin was interpreted in terms of 69% contribution from absorption by tryptophan residues and 31% contribution from absorption by tyrosine residues. The total dipole strength of the ricin band at 280 nm was determined to be (147+/-8) D2 and was consistent with the combined dipole strengths of 10 tryptophan ([11.7+/-1.0] D2) and 23 tyrosine ([1.4+/-0.2] D2) residues. The structure of ricin was used to determine the coupling of the tryptophan residues in ricin. The maximum interaction energy was found to be 424 cm(-1)/epsilon while the average interaction between any two pairs of tryptophan residues was approximately 18 cm(-1)/epsilon. In this study, epsilon is the dielectric constant inside the protein. The fluorescence from ricin, excited at 280 nm, was dominated by fluorescence from tryptophan residues suggesting the presence of energy transfer from tyrosine to tryptophan residues. The absorbance and fluorescence of ricin increased slightly when ricin was denatured in a high concentration of guanidine. Irreversible thermal unfolding of ricin occurred between 65 degrees C and 70 degrees C. (D=3.3364*10(-30) Cm, not SI unit, convenient unit for the magnitude of the electric dipole moment of molecules.).     

The impact of tripodal chelates on water exchange kinetics and mechanisms: a variable temperature and pressure 17O NMR study to clarify the structure-reactivity relationship in [Fe(II)(L)(H2O2](-) complexes

The effect of temperature and pressure on the water exchange reaction of [Fe(II)(NTA)(H2O)2](-) and [Fe(II)(BADA)(H2O)2](-) (NTA = nitrilotriacetate; BADA = beta-alanindiacetate) was studied by 17O NMR spectroscopy. The [Fe(II)(NTA)(H2O)2](-) complex showed a water exchange rate constant, k(ex), of (3.1 +/- 0.4) x 10(6) s(-1) at 298.2 K and ambient pressure. The activation parameters DeltaH( not equal), DeltaS( not equal) and DeltaV( not equal) for the observed reaction are 43.4 +/- 2.6 kJ mol(-1), + 25 +/- 9 J K(-1) mol(-1) and + 13.2 +/- 0.6 cm(3) mol(-1), respectively. For [Fe(II)(BADA)(H2O)2](-), the water exchange reaction is faster than for the [Fe(II)(NTA)(H2O)2](-) complex with k(ex) = (7.4 +/- 0.4) x 10(6) s(-1) at 298.2 K and ambient pressure. The activation parameters DeltaH( not equal), DeltaS( not equal) and DeltaV( not equal) for the water exchange reaction are 40.3 +/- 2.5 kJ mol(-1), + 22 +/- 9 J K(-1) mol(-1) and + 13.3 +/- 0.8 cm(3) mol(-1), respectively. The effect of pressure on the exchange rate constant is large and very similar for both systems, and the numerical values for DeltaV( not equal) suggest in both cases a limiting dissociative (D) mechanism for the water exchange process.     

The absorption spectrum of water near 750 nm by CW-CRDS: contribution to the search of water dimer absorption

The absorption spectrum of natural water vapour around 750 nm has been recorded with a typical sensitivity of 3 x 10(-10) cm(-1) using a cw cavity ring down spectroscopy set up based on a Ti:sapphire laser. The 13 312.4-13 377.7 cm(-1) spectral interval was chosen as it corresponds to the region where water dimer absorption was recently measured (K. Pfeisticker et al., Science, 2003, 300, 2078-2080). The line parameters (wavenumber and intensity) of a total of 286 lines of water vapor were measured by a one by one fit of the lines to a Voigt profile. For the main water isotopologue, 276 lines were measured with line intensities as weak as 5 x 10(-29) cm molecule(-1)i.e. about 50 times smaller than the weakest H(2)16O line intensities included in the 2004 edition of the HITRAN database. On the basis of the predictions of Schwenke and Partridge, all but 16 lines could be assigned to different isotopologues of water (H(2)16O, H(2)18O, and HD16O) present in natural abundance in the sample. A total of 272 energy levels of H(2)16O were determined and rovibrationally assigned to 18 upper vibrational states. Half of them had not been reported previously. The importance of the additional absorbance resulting from the observation of many new weak lines is discussed in relation to the detection of water dimer absorption and compared to the absorbance predicted by Schwenke and Partridge. The quality of the line parameters of water monomer is shown to be of crucial importance to identify the absorbance of the water dimer in the considered region.     

Thermodynamic parameters for the molecular inclusion reaction of dulcin with beta-cyclodextrin. spectrofluorimetric determination of dulcin

The inclusion of dulcin in alpha- and beta-cyclodextrin has been studied by fluorescence spectroscopy. To quantitatively describe complex formation between the beta-cyclodextrin and dulcin, an association constant of 290 M(-1) at 21 degrees was obtained. The thermodynamics associated with the complex formation between dulcin and beta-cyclodextrin in aqueous solution has been studied. The obtained value of DeltaG(0) = -13.7 kJ/mole at 21 degrees , together with DeltaH(0) = -33.6 +/- 2.3 kJ/mole and DeltaS(0) = -67.2 +/-8.3 Jmole(-1) K(-1) indicate that dulcin has a very marked tendency to associate with beta-cyclodextrin in water. The inclusion complex of dulcin in beta-cyclodextrin has been used to determine dulein in the range 0.13-5 mug/ml the method has been applied to determine dulcin in soft drinks.     

Spectra of water dimer from a new ab initio potential with flexible monomers

We report the definition and testing of a new ab initio 12-dimensional potential for the water dimer with flexible monomers. Using our recent accurate CCpol-8s rigid water pair potential [W. Cencek, K. Szalewicz, C. Leforestier, R. van Harrevelt, and A. van der Avoird, Phys. Chem. Chem. Phys. 10, 4716 (2008)] as a reference for the undistorted monomers' geometries, a distortion correction has been added, which was taken from a former flexible-monomer ab initio potential. This correction allows us to retrieve the correct binding energy D(e)=21.0 kJ mol(-1), and leads to an equilibrium geometry in close agreement with the one obtained from benchmark calculations. The kinetic energy operator describing the flexible-monomer water dimer has been expressed in terms of Radau coordinates for each monomer and a recent general cluster polyspherical formulation describing their relative motions. Within this formulation, an adiabatic scheme has been invoked in order to decouple fast (intramolecular) modes and slow (intermolecular) ones. Different levels of approximation were tested, which differ in the way in which the residual potential coupling between the intramolecular modes located on different monomers and the dependence of the monomer rotational constants on the dimer geometry are handled. Accurate calculations of the vibration-rotation-tunneling levels of (H(2)O)(2) and (D(2)O)(2) were performed, which show the best agreement with experiments achieved so far for any water potential. Intramolecular excitations of the two monomers were calculated within two limiting cases, to account for the lack of non-adiabatic coupling between intramolecular modes due to the intermolecular motion. In the first model, the excitation was assumed to stay either on the donor or the acceptor molecule, and to hop between the two moieties upon donor-acceptor interchange. In the second model, the excitation remains on the same molecule whatever is the dimer geometry. Marginal frequency differences, less than 2?cm(-1), were obtained for all modes, and the resulting infrared shifts are in good agreement with experiments.     

Overtone dissociation of peroxynitric acid (HO2NO2): absorption cross sections and photolysis products

Band strengths for the second (3nuOH) and third (4nuOH) overtones of the OH stretch vibration of peroxynitric acid, HO2NO2 (PNA) in the gas-phase were measured using Cavity Ring-Down Spectroscopy (CRDS). Both OH overtone transitions show diffuse smoothly varying symmetrical absorption profiles without observable rotational structure. Integrated band strengths (base e) at 296 K were determined to be S(3nuOH) = (5.7 +/- 1.1) x 10(-20) and S(4nuOH) = (4.9 +/- 0.9) x 10(-21) cm(2) molecule(-1) cm(-1) with peak cross sections of (8.8 +/- 1.7) x 10(-22) and (7.0 +/- 1.3) x 10(-23) cm(2) molecule(-1) at 10086.0 +/- 0.2 cm(-1) and 13095.8 +/- 0.4 cm(-1), respectively, using PNA concentrations measured on line by Fourier-transform infrared and ultraviolet absorption spectroscopy. The quoted uncertainties are 2sigma (95% confidence level) and include estimated systematic errors in the measurements. OH overtone spectra measured at lower temperature, 231 K, showed a narrowing of the 3nuOH band along with an increase in its peak absorption cross section, but no change in S(3nuOH) to within the precision of the measurement (+/-9%). Measurement of a PNA action spectrum showed that HO2 is produced from second overtone photodissociation. The action spectrum agreed with the CRDS absorption spectra. The PNA cross sections determined in this work for 3nuOH and 4nuOH will increase calculated atmospheric photolysis rates of PNA slightly.