Collective solvent coordinates for the infrared spectrum of HOD in D2O based on an ab initio electrostatic map

An ab initio MP2 vibrational Hamiltonian of HOD in an external electrostatic potential parametrized by the electric field and its gradient-tensor is constructed. By combining it with the fluctuating electric field induced by the D(2)O solvent obtained from molecular dynamics simulations, we calculate the infrared absorption of the O-H stretch. The resulting solvent shift and infrared line shape for three force fields (TIP4P, SPC/E, and SW) are in good agreement with the experiment. A collective coordinate response for the solvent effect is constructed by identifying the main electrostatic field and gradient components contributing to the line shape. This allows a realistic stochastic Liouville equation simulation of the line shapes which is not restricted to Gaussian frequency fluctuations.     

Infrared and Raman line shapes of dilute HOD in liquid H2O and D2O from 10 to 90 degrees C

A combined electronic structure/molecular dynamics approach was used to calculate infrared and isotropic Raman spectra for the OH or OD stretches of dilute HOD in D2O or H2O, respectively. The quantities needed to compute the infrared and Raman spectra were obtained from density functional theory calculations performed on clusters, generated from liquid-state configurations, containing an HOD molecule along with 4-9 solvent water molecules. The frequency, transition dipole, and isotropic transition polarizability were each empirically related to the electric field due to the solvent along the OH (or OD) bond, calculated on the H (or D) atom of interest. The frequency and transition dipole moment of the OH (or OD) stretch of the HOD molecule were found to be very sensitive to its instantaneous solvent environment, as opposed to the isotropic transition polarizability, which was found to be relatively insensitive to environment. Infrared and isotropic Raman spectra were computed within a molecular dynamics simulation by using the empirical relationships and semiclassical expressions for the line shapes. The line shapes agree well with experiment over a temperature range from 10 to 90 degrees C.     

Spectral diffusion in a fluctuating charge model of water

We apply the combined electronic structure/molecular dynamics approach of Corcelli, Lawrence, and Skinner [J. Chem. Phys. 120, 8107 (2004)] to the fluctuating charge (SPC-FQ) model of liquid water developed by Rick, Stuart, and Berne [J. Chem. Phys. 101, 6141 (1994)]. For HOD in H(2)O the time scale for the long-time decay of the OD stretch frequency time-correlation function, which corresponds to the time scale for hydrogen-bond rearrangement in the liquid, is about 1.5 ps. This result is significantly longer than the 0.9 ps decay previously calculated for the nonpolarizable SPC/E water model. Our results for the SPC-FQ model are in better agreement with recent vibrational echo experiments.     

Stochastic Liouville equations for hydrogen-bonding fluctuations and their signatures in two-dimensional vibrational spectroscopy of water

The effects of hydrogen-bond forming and breaking kinetics on the linear and coherent third-order infrared spectra of the OH stretch of HOD in D2O are described by Markovian, not necessarily Gaussian, fluctuations and simulated using the stochastic Liouville equations. Slow (0.5 ps) fluctuations are represented by a collective electrostatic coordinate, whereas fast (<100 fs) frequency fluctuations are described using either a second collective electrostatic coordinate or a four-state jump (FSJ) model for hydrogen-bonding configurations. Parameters for both models were obtained using a 1-ns molecular-dynamics trajectory calculated using the TIP4P force field combined with an electrostatic ab initio map. The asymmetry of the photon-echo spectra (larger linewidth on the blue side than on the red side) predicted by the FSJ is in better agreement with recent experiments.     

Dynamics of water probed with vibrational echo correlation spectroscopy

Vibrational echo correlation spectroscopy experiments on the OD stretch of dilute HOD in H(2)O are used to probe the structural dynamics of water. A method is demonstrated for combining correlation spectra taken with different infrared pulse bandwidths (pulse durations), making it possible to use data collected from many experiments in which the laser pulse properties are not identical. Accurate measurements of the OD stretch anharmonicity (162 cm(-1)) are presented and used in the data analysis. In addition, the recent accurate determination of the OD vibrational lifetime (1.45 ps) and the time scale for the production of vibrational relaxation induced broken hydrogen bond "photoproducts" ( approximately 2 ps) aid in the data analysis. The data are analyzed using time dependent diagrammatic perturbation theory to obtain the frequency time correlation function (FTCF). The results are an improved FTCF compared to that obtained previously with vibrational echo correlation spectroscopy. The experimental data and the experimentally determined FTCF are compared to calculations that employ a polarizable water model (SPC-FQ) to calculate the FTCF. The SPC-FQ derived FTCF is much closer to the experimental results than previously tested nonpolarizable water models which are also presented for comparison.     

Two-dimensional infrared spectroscopy of isotope-diluted ice Ih

We present experimental 2D IR spectra of isotope diluted ice Ih (i.e., the OH stretch mode of HOD in D(2)O and the OD stretch mode of HOD in H(2)O) at T = 80 K. The main spectral features are the extremely broad 1-2 excited state transition, much broader than the corresponding 0-1 groundstate transition, as well as the presence of quantum beats. We do not observe any inhomogeneous broadening that might be expected due to proton disorder in ice Ih. Complementary, we perform simulations in the framework of the Lippincott-Schroeder model, which qualitatively reproduce the experimental observations. We conclude that the origin of the observed line shape features is the coupling of the OH-vibrational coordinate with crystal phonons and explain the beatings as a coherent oscillation of the O···O hydrogen bond degree of freedom.     

The (CH2)2O-H2O hydrogen bonded complex. Ab Initio calculations and Fourier transform infrared spectroscopy from neon matrix and a new supersonic jet experiment coupled to the infrared AILES beamline of synchrotron SOLEIL

A series of hydrogen bonded complexes involving oxirane and water molecules have been studied. In this paper we report on the vibrational study of the oxirane-water complex (CH(2))(2)O-H(2)O. Neon matrix experiments and ab initio anharmonic vibrational calculations have been performed, providing a consistent set of vibrational frequencies and anharmonic coupling constants. The implementation of a new large flow supersonic jet coupled to the Bruker IFS 125 HR spectrometer at the infrared AILES beamline of the French synchrotron SOLEIL (Jet-AILES) enabled us to record first jet-cooled Fourier transform infrared spectra of oxirane-water complexes at different resolutions down to 0.2 cm(-1). Rovibrational parameters and a lower bound of the predissociation lifetime of 25 ps for the v(OH)(b) = 1 state have been derived from the rovibrational analysis of the ν(OH)(b) band contour recorded at respective rotational temperatures of 12 K (Jet-AILES) and 35 K (LADIR jet).     

H2O(HOD) + Cl→HCl(DCl) + OH(OD)反应动态学的理论研究

用从头算方法, 获得了H2O + Cl→HCl + OH(R1), HOD +Cl→DCl + OH(R2), HOD + Cl→HCl + OD(R3)反应的内禀反应坐标(IRC)。根据传统过渡态、变分过渡态理论及相应的隧道效应校正, 计算了反应的速率常数。对已有实验速率常数值的R1反应, 我们计算的结果和实验一致。根据Truhlar的振动选态公式, 分别讨论了激发HOD中OH, OD振动模式对反应速率的影响,得到激发HOD中的OH振动模式将有利于产物OD + HCl生成, 和实验的结论相一致。     

Isotope effects in liquid water by infrared spectroscopy. V. A sea of OH4 of C2v symmetry

The two water gas OH stretch vibrations that absorb in the infrared (IR) near 3700 cm(-1) are redshifted to near 3300 cm(-1) upon liquefaction. The bathochromic shift is due to the formation of four H-bonds: two are from the labile hydrogen atoms to neighbors and two are received from neighbors by the oxygen free electron pairs. Therefore, the water oxygen atom is surrounded by four hydrogen atoms, two of these make covalent bonds that make H-bonds and two are oxygen H-bonded. However, these permute at rate in the ps range. When the water molecules are isolated in acetonitrile (MeCN) or acetone (Me(2)CO), only the labile hydrogen atoms make H-bonds with the solvent. The bathochromic shift of the OH stretch bands is then almost 130 cm(-1) with, however, the asymmetric (ν(3)) and symmetric (ν(1)) stretch bands maintained. When more water is added to the solutions, the oxygen lone doublets make H-bonds with the available labile hydrogen atoms from neighboring water molecules. With one bond accepted, the bathochromic shift is further displaced by almost 170 cm(-1). When the second oxygen doublet is filled, another bathochromic shift by almost 100 cm(-1) is observed. The total bathochromic shift is near 400 cm(-1) with a full width at half height of near 400 cm(1). This is the case of pure liquid water. Notwithstanding the shift and the band broadness, the ν(3) and ν(1) band individualities are maintained with, however, added satellite companions that come from the far IR (FIR) absorption. These added to the fundamental bands are responsible for the band broadness and almost featureless shape of the massive OH stretch absorption of liquid water. Comparison of light and heavy water mixture spectra indicates that the OH and OD stretch regions show five different configurations: OH(4); OH(3)D; OH(2)D(2); OHD(3); and OD(4) [J. Chem. Phys. 116, 4626 (2002)]. The comparison of the OH bands of OH(4) with that of OHD(3) indicates that the main component in OHD(3) is ν(OH), whereas in OH(4) two main components are present: ν(3) and ν(1). Similar results are obtained for the OD bands of OD(4) and ODH(3). These results indicate that the C(2) (v) symmetry of H(2)O and D(2)O is preserved in the liquid and aqueous solutions whereas C(s) is that of HDO.     

Multidimensional infrared spectroscopy of water. II. Hydrogen bond switching dynamics

We use multidimensional infrared spectroscopy of the OH stretch of HOD in D2O to measure the interconversion of different hydrogen bonding environments. The OH stretching frequency distinguishes hydrogen bonded (HB) and non-hydrogen-bonded (NHB) configurations by their absorption on the low (red) and high (blue) sides of the line shape. Measured asymmetries in the two dimensional infrared OH line shapes are manifestations of the fundamentally different spectral relaxations of HB and NHB. HB oscillators exhibit coherent oscillations within the hydrogen-bonded free energy well before undergoing activated barrier crossing, resulting in the exchange of hydrogen bonded partners. Conversely, NHB oscillators rapidly return to HB frequencies within 150 fs. These results support a picture where NHB configurations are only visited transiently during large fluctuations about a hydrogen bond or during the switching of hydrogen bonding partners. The results are not consistent with the presence of entropically stabilized dangling hydrogen bonds or a conceptual picture of water as a mixture of environments with varying hydrogen bond strength separated by barriers >kT.     

H+ versus D+ transfer from HOD+ to CO2: bond-selective chemistry and the anomalous effect of bending excitation

Reactions of HOD(+) with CO(2) have been studied for HOD(+) in its ground state, and with one quantum of excitation in each of its vibrational modes: (001)--predominantly OH stretch, 0.396 eV; (010)--bend, 0.153 eV; and (100)--predominantly OD stretch, 0.293 eV. Integral cross sections and product recoil velocities were recorded for collision energies from threshold to 3 eV. The cross sections for both H(+) and D(+) transfer rise with increasing collision energy from threshold to ～1 eV, then become weakly dependent of the collision energy. All three vibrational modes enhance the total reactivity, but quite mode specifically. The H(+) transfer reaction is enhanced by OH stretch excitation, whereas OD stretch excitation has little effect. Conversely, the D(+) transfer reaction is enhanced by OD stretch excitation, while the OH stretch has little effect. Excitation of the bend strongly enhances both channels. The effects of the stretch excitations are consistent with previous studies of neutral HOD mode-selective chemistry, and can be at least qualitatively understood in terms of a late barrier to product formation. The fact that bend excitation produces the largest overall enhancement is surprising, because this is the lowest energy excitation, and is not obviously connected with the reaction coordinates for either H(+) or D(+) transfer. A rationalization in terms of the effects of water distortion on the potential surface is proposed.     

Orientational dynamics of water confined on a nanometer length scale in reverse micelles

The time-resolved orientational anisotropies of the OD hydroxyl stretch of dilute HOD in H(2)O confined on a nanometer length scale in sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles are studied using ultrafast infrared polarization and spectrally resolved pump-probe spectroscopy, and the results are compared to the same experiments on bulk water. The orientational anisotropy data for three water nanopool sizes (4.0, 2.4, and 1.7 nm) can be fitted well with biexponential decays. The biexponential decays are analyzed using a wobbling-in-a-cone model that involves fast orientational diffusion within a cone followed by slower, full orientational relaxation. The data provide the cone angles, the diffusion constants for motion within the cones, and the final diffusion constants as a function of the nanopool size. The two processes can be interpreted as a local angular fluctuation of the OD and a global hydrogen bond network rearrangement process. The trend in the relative amplitudes of the long and short exponential decays suggest an increasing rigidity as the nanopool size decreases. The trend in the long decay constants indicates a longer hydrogen bond network rearrangement time with decreasing reverse micelle size. The anisotropy measurements for the reverse micelles studied extrapolate to approximately 0.33 rather than the ideal value of 0.4, suggesting the presence of an initial inertial component in the anisotropy decay that is too fast to resolve. The very fast decay component is consistent with initial inertial orientational motion that is seen in published molecular-dynamics simulations of water in AOT reverse micelles. The angle over which the inertial orientational motion occurs is determined. The results are in semiquantitative agreement with the molecular-dynamics simulations.     

Infrared measurements and calculations on H2O.HO

We have measured the infrared spectrum of H2O.HO in argon matrices at 11.5 +/- 0.5 K. We have also calculated the vibrational frequencies and intensities of the H2O.HO complex. As a result of these measurements and calculations, we have assigned a previously unassigned absorption band at 3442.1 cm-1 to the OH stretch in the radical complexed to the water molecule. This absorption originates from a complex that is situated in a different site within the argon matrix to those absorptions already assigned to this vibration at 3452.2 and 3428.0 cm-1. We observe a decrease in intensity of the OH radical stretching vibration of the H2O.HO complex upon isotopic substitution of D for H that agrees well with our calculations.     

Hofmeister anionic effects on hydration electric fields around water and peptide

Specific ion effects on water dynamics and local solvation structure around a peptide are important in understanding the Hofmeister series of ions and their effects on protein stability in aqueous solution. Water dynamics is essentially governed by local hydrogen-bonding interactions with surrounding water molecules producing hydration electric field on each water molecule. Here, we show that the hydration electric field on the OD bond of HOD molecule in water can be directly estimated by measuring its OD stretch infrared (IR) radiation frequency shift upon increasing ion concentration. For a variety of electrolyte solutions containing Hofmeister anions, we measured the OD stretch IR bands and estimated the hydration electric field on the OD bond to be about a hundred MV∕cm with standard deviation of tens of MV∕cm. As anion concentration increases from 1 to 6 M, the hydration electric field on the OD bond decreases by about 10%, indicating that the local H-bond network is partially broken by dissolved ions. However, the measured hydration electric fields on the OD bond and its fluctuation amplitudes for varying anions are rather independent on whether the anion is a kosmotrope or a chaotrope. To further examine the Hofmeister effects on H-bond solvation structure around a peptide bond, we examined the amide I' and II' mode frequencies of N-methylacetamide in various electrolyte D(2)O solutions. It is found that the two amide vibrational frequencies are not affected by ions, indicating that the H-bond solvation structure in the vicinity of a peptide remains the same irrespective of the concentration and character of ions. The present experimental results suggest that the Hofmeister anionic effects are not caused by direct electrostatic interactions of ions with peptide bond or water molecules in its first solvation shell. Furthermore, even though the H-bond network of water is affected by ions, thus induced change of local hydration electric field on the OD bond of HOD is not in good correlation with the well-known Hofmeister series. We anticipate that the present experimental results provide an important clue about the Hofmeister effect on protein structure and present a discussion on possible alternative mechanisms.     

Three-point frequency fluctuation correlation functions of the OH stretch in liquid water

Characterizing the dynamics of the OH stretch in isotopically substituted liquid water (HOD in D(2)O) in terms of three-point frequency fluctuation correlation functions and joint probability densities shows that dynamics during hydrogen bond rearrangements occur primarily along a coordinate which is perpendicular to the spectroscopic coordinate. Molecular dynamics simulations show that three-point correlation functions are sensitive to this motion, unlike two-point correlation functions, and can select sets of trajectories which linger in the area of the transition state. Three-dimensional-infrared correlation spectroscopy could potentially measure these dynamics, though motional narrowing significantly changes the shape of the resulting spectra.     

Jet cooled spectroscopy of H2DO+: Barrier heights and isotope-dependent tunneling dynamics from H3O+ to D3O+

The first high resolution spectroscopic data for jet cooled H2DO+ are reported, specifically via infrared laser direct absorption in the OH stretching region with a slit supersonic jet discharge source. Transitions sampling upper (0-) and lower (0+) tunneling states for both symmetric (nu1+ <-- 0+, nu1- <-- 0-, and nu1- <-- 0+) and antisymmetric (nu3+ <-- 0+ and nu3- <-- 0-) OH stretching bands are observed, where +/- refers to wave function reflection symmetry with respect to the planar umbrella mode transition state. The spectra can be well fitted to a Watson asymmetric top Hamiltonian, revealing band origins and rotational constants for benchmark comparison with high-level ab initio theory. Of particular importance are detection and assignment of the relatively weak band (nu1- <-- 0+) that crosses the inversion tunneling gap, which is optically forbidden in H3O+ or D3O+, but weakly allowed in H2DO+ by lowering of the tunneling transition state symmetry from D(3h) to C(2v). In conjunction with other H2DO+ bands, this permits determination of the tunneling splittings to within spectroscopic precision for each of the ground [40.518(10) cm(-1)], nu1 = 1 [32.666(6) cm(-1)], and nu3 = 1 [25.399(11) cm(-1)] states. A one-dimensional zero-point energy corrected potential along the tunneling coordinate is constructed from high-level ab initio CCSD(T) calculations (AVnZ, n = 3,4,5) and extrapolated to the complete basis set limit to extract tunneling splittings via a vibrationally adiabatic treatment. Perturbative scaling of the potential to match splittings for all four isotopomers permits an experimental estimate of DeltaV0 = 652.9(6) cm(-1) for the tunneling barrier, in good agreement with full six-dimensional ab initio results of Rajamaki, Miani, and Halonen (RMH) [J. Chem. Phys. 118, 10929 (2003)]. (DeltaV0 (RMH) = 650 cm(-1)). The 30%-50% decrease in tunneling splitting observed upon nu1 and nu3 vibrational excitations arises from an increase in OH stretch frequencies at the planar transition state, highlighting the transition between sp2 and sp3 hybridizations of the OHD bonds as a function of inversion bending angle.     

Dispersion of the Raman depolarization ratio of HDO in water and heavy water from 295 to 368 K, and from concentrated NaClO4D2OH2O

The dispersion of the Raman depolarization ratio rho(L) was measured for HDO in H(2)O and in D(2)O. rho(L) for the decoupled OD stretch displays a maximum at 2575 +/- 15 cm(-1) at 296 K and a minimum at 2675 +/- 15 cm(-1), in agreement with the isosbestic point 2570 +/- 10 cm(-1), and the enthalpy dispersion maximum, 2650-2675 cm(-1), respectively. However, three extrema were uncovered in rho(L) for the OH stretch of HDO in D(2)O, and their positions agree with the frequencies of a minimum and a maximum in the enthalpy dispersion and with the isosbestic frequency. The frequency of the rho(L) maximum (OH stretch) lies just above the frequency corresponding to the joint angle-frequency probability maximum. [Lawrence and Skinner, J. Chem. Phys. 118, 264 (2003)]. The low- and high-frequency minima in rho(L) (OH stretch), correspond, respectively, to very strong H-bonds, and extremely weak, long, bent H bonds. The frequencies of the maxima and minima in rho(L) for the decoupled OH and OD stretches are independent of temperature within experimental error between 295 and 368 K. rho(L) was also measured for the OD stretch from saturated NaClO(4) in D(2)OH(2)O; it displays a maximum at 2560 +/- 20 cm(-1) and a sharp minimum at 2650 +/- 5 cm(-1). The shape of the dispersion of (betaalpha)(2) approximately rho(L) for HDO in D(2)O was calculated with the aid of the molecular dynamics results of Lawrence and Skinner. beta(2) is the anisotropic polarizability and alpha is the isotropic polarizability. A maximum resulted in the calculated dispersion at 3400 +/- 10 cm(-1), in excellent agreement with the measured maximum of 3395 +/- 15 cm(-1). The H-bond angles decrease far below 180 degrees as the OH-stretching frequency increases to 3700 cm(-1) and above. Such small H-bond angles, and very large O-O distances, are tantamount to broken H-bonds and are thought to produce the minimum in rho(L) near 2650 cm(-1).     

Rotational motion in liquid water is anisotropic: a nuclear magnetic resonance and molecular dynamics simulation study

Experimental NMR measurements of the deuterium and (17)O T(1) relaxation times in deuterium-enriched liquid water have been performed from 275 to 350 K. These relaxation times can yield rotational correlation times of appropriate molecule-fixed unit vectors if the quadrupole coupling constants and asymmetry parameters are known. We determine the latter from ab initio studies of water clusters and experimental chemical shift measurements. We find that the rotational correlation time for the OD bond vector in D(2)(16)O varies from 5.8 ps at 275 K to 0.86 ps at 350 K, and that the rotational correlation time for the out-of-plane vector of dilute D(2)(17)O in D(2)(16)O varies from 4.4 ps at 275 K to 0.64 ps at 350 K. These results indicate that the rotational motion of water is anisotropic. Molecular dynamics simulations of liquid water are in good agreement with these experiments at the higher temperatures, but the simulation results are considerably faster than experiment at the lower temperatures.     

The relaxation of OH (v=1) and OD (v=1) by H2O and D2O at temperatures from 251 to 390 K

We report rate coefficients for the relaxation of OH(v=1) and OD(v=1) by H2O and D2O as a function of temperature between 251 and 390 K. All four rate coefficients exhibit a negative dependence on temperature. In Arrhenius form, the rate coefficients for relaxation (in units of 10(-12) cm3 molecule-1 s-1) can be expressed as: for OH(v=1)+H2O between 263 and 390 K: k=(2.4+/-0.9) exp((460+/-115)/T); for OH(v=1)+D2O between 256 and 371 K: k=(0.49+/-0.16) exp((610+/-90)/T); for OD(v=1)+H2O between 251 and 371 K: k=(0.92+/-0.16) exp((485+/-48)/T); for OD(v=1)+D2O between 253 and 366 K: k=(2.57+/-0.09) exp((342+/-10)/T). Rate coefficients at (297+/-1 K) are also reported for the relaxation of OH(v=2) by D2O and the relaxation of OD(v=2) by H2O and D2O. The results are discussed in terms of a mechanism involving the formation of hydrogen-bonded complexes in which intramolecular vibrational energy redistribution can occur at rates competitive with re-dissociation to the initial collision partners in their original vibrational states. New ab initio calculations on the H2O-HO system have been performed which, inter alia, yield vibrational frequencies for all four complexes: H2O-HO, D2O-HO, H2O-DO and D2O-DO. These data are then employed, adapting a formalism due to Troe (J. Troe, J. Chem. Phys., 1977, 66, 4758), in order to estimate the rates of intramolecular energy transfer from the OH (OD) vibration to other modes in the complexes in order to explain the measured relaxation rates-assuming that relaxation proceeds via the hydrogen-bonded complexes.