The bend angle of water in ice Ih and liquid water: The significance of implementing the nonlinear monomer dipole moment surface in classical interaction potentials

The implementation of the physically accurate nonlinear dipole moment surface of the water monomer in the context of the Thole-type, polarizable, flexible interaction potential results in the only classical potential, which, starting from the gas phase value for the bend angle (104.52 degrees), reproduces its experimentally observed increase in the ice Ih lattice and in liquid water. This is in contrast to all other classical potentials to date, which predict a decrease of the monomer bend angle in ice Ih and in liquid water with respect to the gas phase monomer value. Simulations under periodic boundary conditions of several supercells consisting of up to 288 molecules of water used to sample the proton disorder in the ice Ih lattice yield an average value of vartheta(HOH)(I(h))=108.4 degrees +/-0.2 degrees for the minimized structures (T=0 K) and 108.1 degrees +/-2.8 degrees at T=100 K. Analogous simulations for liquid water predict an average value of vartheta(HOH)(liquid)=106.3 degrees +/-4.9 degrees at T=300 K. The increase of the monomer bend angle of water in condensed environments is attributed to the use of geometry-dependent charges that are used to describe the nonlinear character of the monomer's dipole moment surface. Our results suggest a new paradigm in the development of classical interaction potential models of water that can be used to describe condensed aqueous environments.     

Proton ordering in cubic ice and hexagonal ice; a potential new ice phase--XIc

Ordinary water ice forms under ambient conditions and has two polytypes, hexagonal ice (Ih) and cubic ice (Ic). From a careful comparison of proton ordering arrangements in Ih and Ic using periodic density functional theory (DFT) and diffusion Monte Carlo (DMC) approaches, we find that the most stable arrangement of water molecules in cubic ice is isoenergetic with that of the proton ordered form of hexagonal ice (known as ice XI). We denote this potential new polytype of ice XI as XIc and discuss a possible route for preparing ice XIc.     

Simulations of proton order and disorder in ice Ih

Computer simulations of ice Ih with different proton orientations are presented. Simulations of proton disordered ice are carried out using a Monte Carlo method which samples over proton degree of freedom, allowing for the calculation of the dielectric constant and for the examination of the degree of proton disorder. Simulations are also presented for two proton ordered structures of ice Ih, the ferroelectric Cmc2(1) structure or ice XI and the antiferroelectric Pna2(1) structure. These simulations indicate that a transition to a proton ordered phase occurs at low temperatures (below 80 K). The symmetry of the ordered phase is found to be dependent on the water potential. The stability of the two proton ordered structures is due to a balance of short-ranged interactions which tend to stabilize the Pna2(1) structure and longer-range interactions which stabilize the Cmc2(1) structure.     

Isotope effects in ice Ih: a path-integral simulation

Ice Ih has been studied by path-integral molecular dynamics simulations, using the effective q-TIP4P/F potential model for flexible water. This has allowed us to analyze finite-temperature quantum effects in this solid phase from 25 to 300 K at ambient pressure. Among these effects we find a negative thermal expansion of ice at low temperatures, which does not appear in classical molecular dynamics simulations. The compressibility derived from volume fluctuations gives results in line with experimental data. We have analyzed isotope effects in ice Ih by considering normal, heavy, and tritiated water. In particular, we studied the effect of changing the isotopic mass of hydrogen on the kinetic energy and atomic delocalization in the crystal as well as on structural properties such as interatomic distances and molar volume. For D(2)O ice Ih at 100 K we obtained a decrease in molar volume and intramolecular O-H distance of 0.6% and 0.4%, respectively, as compared to H(2)O ice.     

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.     

Raman spectra of proton ordered phase XI of ICE I. Translational vibrations below 350 cm(-1)

Polarized Raman spectra from single crystals of ice XI (proton ordered phase of ice Ih) were measured and assigned for the modes below 350 cm(-1) in the translational vibration region. In contrast to the proton disordered ice Ih, the spectra in ice XI show clear polarization dependence and several new peaks are observed. Most of the vibrational modes were successfully assigned by the simplified point mass model with the symmetry C(2v) (12)(Cmc2(1)) and by the depolarization effect. In particular, LO-TO splitting of the mode near 240 cm(-1) was experimentally confirmed for the first time, which indicates that the long range force effect appears distinctly in ice XI.     

Transient absorption of vibrationally excited ice Ih

The ultrafast dynamics of HDO:D2O ice Ih at 180 K is studied by midinfrared ultrafast pump-probe spectroscopy. The vibrational relaxation of HDO:D2O ice is observed to proceed via an intermediate state, which has a blueshifted absorption spectrum. Polarization resolved measurements reveal that the intermediate state is part of the intramolecular relaxation pathway of the HDO molecule. In addition, slow dynamics on a time scale of the order of 10-100 ps is observed, related to thermally induced collective reorganizations of the ice lattice. The transient absorption line shape is analyzed within a Lippincott-Schroeder model for the OH-stretch potential. This analysis identifies the main mechanism behind the strong spectral broadening of the v(OH)=1-->2 transition.     

Infrared and Raman line shapes for ice Ih. II. H2O and D2O

We present a theoretical study of infrared and Raman line shapes of polycrystalline and single crystal ice Ih, for both water and heavy water, at 1, 125, and 245 K. Our calculations involve a mixed quantum/classical approach, a new water simulation model with explicit three-body interactions, transition frequency and dipole maps, and intramolecular and intermolecular vibrational coupling maps. Our theoretical spectra are in reasonable agreement with experimental spectra (available only near the two higher temperatures). We trace the origins of the different spectral peaks to weak and strong intermolecular couplings. We also discuss the delocalization of the vibrational eigenstates in terms of the competing effects of disorder and coupling.     

Sticking of CO to crystalline and amorphous ice surfaces

We present results of classical trajectory calculations on the sticking of hyperthermal CO to the basal plane (0001) face of crystalline ice Ih and to the surface of amorphous ice Ia. The calculations were performed for normal incidence at a surface temperature Ts = 90 K for ice Ia, and at Ts = 90 and 150 K for ice Ih. For both surfaces, the sticking probability can be fitted to a simple exponentially decaying function of the incidence energy, Ei: Ps = 1.0e(-Ei(kJ/mol)/90(kJ/mol)) at Ts = 90 K. The energy transfer from the impinging molecule to the crystalline and the amorphous surface is found to be quite efficient, in agreement with the results of molecular beam experiments on the scattering of the similar molecule, N2, from crystalline and amorphous ice. However, the energy transfer is less efficient for amorphous than for crystalline ice. Our calculations predict that the sticking probability decreases with Ts for CO scattering from crystalline ice, as the energy transfer from the impinging molecule to the warmer surfaces becomes less efficient. At high Ei (up to 193 kJ/mol), no surface penetration occurs in the case of crystalline ice. However, for CO colliding with the amorphous surface, a penetrating trajectory was observed to occur into a large water pore. The molecular dynamics calculations predict that the average potential energy of CO adsorbed to ice Ih is -10.1 +/- 0.2 and -8.4 +/- 0.2 kJ/mol for CO adsorbed to ice Ia. These values are in agreement with previous experimental and theoretical data. The distribution of the potential energy of CO adsorbed to ice Ia was found to be wider (with a standard deviation sigma of 2.4 kJ/mol) than that of CO interacting with ice Ih (sigma = 2.0 kJ/mol). In collisions with ice Ia, the CO molecules scatter at larger angles and over a wider distribution of angles than in collisions with ice Ih.     

Vibrational modes of hydrogens in the proton ordered phase XI of ice: Raman spectra above 400 cm(-1)

Polarized Raman spectra of the proton ordered phase of ice Ih, i.e., ice XI, were measured above 400 cm(-1) in the range of librational, bending, and stretching vibrations. Vibrational modes in ice XI, of which symmetry is C(2v) (12)(Cmc2(1)), were discussed from the group theoretical point of view. In the librational mode spectra below 1200 cm(-1), several new peaks and clear polarization dependencies were observed. Assignments of the librational modes agree reasonably well with the recent MD calculations by Iwano et al. (J. Phys. Soc. Jpn. 79, 063601 (2010)). In contrast, the spectra for bands above 1200 cm(-1) show no distinct polarization dependencies and the spectra resemble those in ice Ih. In ice XI, however, fine structure composed of several weak peaks appear on the broad bending and the combination band. No direct evidence of the LO-TO splitting of the ν(3) anti-symmetric stretching mode was obtained. It is contrary to the case of the translational modes Abe and Shigenari (J. Chem. Phys. 134, 104506 (2011)). Present results suggest that the influence of the proton ordering in ice XI is weaker than the effect of inter- and intra-molecular couplings in the stretching vibrations of ice Ih.     

Intra- and intermolecular hydrogen bonding in formohydroxamic acid complexes with water and ammonia: infrared matrix isolation and theoretical study

The complexes of formohydroxamic acid with water and ammonia have been studied using FTIR matrix isolation spectroscopy and MP2 calculations with a 6-311++G(2d,2p) basis set. The analysis of the experimental spectra of the HCONHOH/H₂O(NH₃)/Ar matrixes indicates formation of strongly hydrogen-bonded complexes in which the NH group of formohydroxamic acid acts as a proton donor toward the oxygen atom of water or the nitrogen atom of ammonia. The NH stretching vibration of formohydroxamic acid exhibits 150 cm⁻¹ red shift in the complex with water and 443 cm⁻¹ red shift in the complex with ammonia as compared to the NH stretch of the HCONHOH monomer. The theoretical calculations indicate stability of five isomers for the water complex and three isomers for the ammonia complex. The most stable are the cyclic structures in which the water or ammonia molecules are inserted within the intramolecular hydrogen bond of the formohydroxamic acid molecule and act as proton donors for the CO group and proton acceptors for the OH group of the formohydroxamic acid molecule. In spite of their stability the cyclic structures have not been observed in the matrixes which indicates high energy barrier for their formation, the reaction of complex formation is under kinetic and not thermodynamic control.     

基于异噁唑酮类份菁染料的激发态分子内质子转移的研究

运用量子化学理论计算方法研究了3-甲基-4-(1H-吲哚-3-次甲基)-异噁唑-5-酮(A)及其衍生物份菁染料的激发态分子内质子转移性质.研究表明:在基态3种染料AH(R=H),AO(R=—O(H3))和AP(R=—O(H2Ph))只存在酮式构型,在激发态AH与AP存在酮式和烯醇式2种构型,而AO存在酮式、烯醇式和仲胺式3种构型.红外光谱表明化合物从基态跃迁到激发态存在分子内的氢键增强作用,势能曲线显示激发态的质子转移为放热反应且能垒较低,通过分析电子光谱得到具有较大斯托克位移的激发态分子内质子转移的荧光发射峰,前线分子轨道理论计算进一步说明了其质子转移的发生过程.     

Azide-water intermolecular coupling measured by two-color two-dimensional infrared spectroscopy

We utilize two-color two-dimensional infrared spectroscopy to measure the intermolecular coupling between azide ions and their surrounding water molecules in order to gain information about the nature of hydrogen bonding of water to ions. Our findings indicate that the main spectral contribution to the intermolecular cross-peak comes from population transfer between the asymmetric stretch vibration of azide and the OD-stretch vibration of D(2)O. The azide-bound D(2)O bleach/stimulated emission signal, which is spectrally much narrower than its linear absorption spectrum, shows that the experiment is selective to solvation shell water molecules for population times up to ~500 fs. The waters around the ion are present in an electrostatically better defined environment. Afterwards, ~1 ps, the sample thermalizes and selectivity is lost. On the other hand, the excited state absorption signal of the azide-bound D(2)O is much broader. The asymmetry in spectral width between bleach/stimulated emission versus excited absorption has been observed in very much the same way for isotope-diluted ice Ih, where it has been attributed to the anharmonicity of the OD potential.     

An application of flexible constraints in Monte Carlo simulations of the isobaric--isothermal ensemble of liquid water and ice Ih with the polarizable and flexible mobile charge densities in harmonic oscillators model

The method of flexible constraints was implemented in a Monte Carlo code to perform numerical simulations of liquid water and ice Ih in the constant number of molecules, volume, and temperature and constant pressure, instead of volume ensembles, using the polarizable and flexible mobile charge densities in harmonic oscillators (MCDHO) model. The structural and energetic results for the liquid at T=298 K and rho=997 kg m(-3) were in good agreement with those obtained from molecular dynamics. The density obtained at P=1 atm with flexible constraints, rho=1008 kg m(-3), was slightly lower than with the classical sampling of the intramolecular vibrations, rho=1010 kg m(-3). The comparison of the structures and energies found for water hexamers and for ice Ih with six standard empirical models to those obtained with MCDHO, show this latter to perform better in describing water far from ambient conditions: the MCDHO minimum lattice energy, density, and lattice constants were in good agreement with experiment. The average angle HOH of the water molecule in ice was predicted to be slightly larger than in the liquid, yet 1.2% smaller than the experimental value.     

Wetting of mixed OHH(2)O layers on Pt(111)

We describe the effect of growth temperature and OHH(2)O composition on the wetting behavior of Pt(111). Changes to the desorption rate of ice films were measured and correlated to the film morphology using low energy electron diffraction and thermal desorption of chloroform to measure the area of multilayer ice and monolayer OHH(2)O exposed. Thin ice films roughen, forming bare (radical39 x radical39)R16 degrees water monolayer and ice clusters. The size of the clusters depends on growth temperature and determines their kinetic stability, with the desorption rate decreasing when larger clusters are formed by growth at high temperature. Continuous films of more than approximately 50 layers thick stabilize an ordered incommensurate ice film that does not dewet. OH coadsorption pins the first layer into registry with Pt, forming an ordered hexagonal (OH+H(2)O) structure with all the H atoms involved in hydrogen bonding. Although this layer has a similar honeycomb OH(x) skeleton to ice Ih, it is unable to reconstruct to match the bulk ice lattice parameter and does not form a stable wetting layer. Water aggregates to expose bare monolayer (OH+H(2)O), forming bulk ice crystallites whose size depend on preparation temperature. Increasing the proportion of water in the first layer provides free OH groups which stabilize the multilayer. The factors influencing multilayer wetting are discussed using density functional theory calculations to compare water adsorption on top of (OH+H(2)O) and on simple models for commensurate water structures. We show that both the (OH+H(2)O) structure and "H-down" water layers are poor proton acceptors, bonding to the first layer being enhanced by the presence of free OH groups. Formation of an ordered ice multilayer requires a water-metal interaction sufficient to wet the surface, but not so strong as to prevent the first layer relaxing to stabilize the interface between the metal and bulk ice.     

Pressure amorphized ices--an atomistic perspective

We offer our viewpoint on the nature of amorphous ices produced by pressurization of crystalline ice Ih and the inter-relationship between them from an atomistic perspective. We argue that the transformation of high density amorphous (HDA) ice from crystalline ice is due to a mechanical process arising from the instability of the ice Ih structure. The densification of HDA upon thermal annealing under pressure is a relaxation process. The conversion of the densified amorphous ice to a lower density form (LDA) upon the release of pressure can be attributed to a similar process. It is speculated that amorphous ices are metastable frustrated structures due to the large activation barriers associated with proton reorientation in the formation of the underlying stable crystalline ice polymorphs.     

Formation of high density amorphous ice by decompression of ice VII and ice VIII at 135 K

Monte Carlo computer simulations of ice VII and ice VIII phases have been undertaken using the four-point transferable intermolecular potential model of water. By following thermodynamic paths similar to those used experimentally, ice is decompressed resulting in an amorphous phase. These phases are compared to the high density amorphous phase formed upon compression of ice Ih and are found to have very similar structures. By cooling liquid water along the water/Ih melting line a high density amorphous phase was also generated.     

Quantum effects in ice Ih

Quantum and classical simulations are carried out on ice Ih over a range of temperatures utilizing the TIP4P water model. The rigid-body centroid molecular dynamics method employed allows for the investigation of equilibrium and dynamical properties of the quantum system. The impact of quantization on the local structure, as measured by the radial and spatial distribution functions, as well as the energy is presented. The effects of quantization on the lattice vibrations, associated with the molecular translations and librations, are also reported. Comparison of quantum and classical simulation results indicates that shifts in the average potential energy are equivalent to rising the temperature about 80 K and are therefore non-negligible. The energy shifts due to quantization and the quantum mechanical uncertainties observed in ice are smaller than the values previously reported for liquid water. Additionally, we carry out a comparative study of melting in our classical and quantum simulations and show that there are significant differences between classical and quantum ice.     

The photodissociation of the water dimer in the A band: a twelve-dimensional quasiclassical study

The quasiclassical absorption spectrum of the water dimer in the A band was calculated taking into account motion in all degrees of freedom of the system. The ab initio excited state potentials employed were interpolated by the modified Shepard interpolation method using QMRCI energies and state-averaged MCSCF gradients and Hessians. The ground state vibrational wavefunction was variationally calculated using an adiabatic separation between the high and low frequency normal modes of the system. The calculated spectrum of water dimer shows a clear blueshift with respect to the monomer, but also a small red tail, in agreement with the prediction by Harvey et al. [J. Chem. Phys. 109, 8747 (1998)]. Previous three-dimensional model studies of the photodissociation of the water dimer by Valenzano et al. [J. Chem. Phys. 123, 034303 (2005)] did not show this red tail. A thorough analysis of the dependence of the spectrum on the modes coupled explicitly in the calculation of the spectrum shows that the red tail is due to coupling between the intramolecular stretch vibrations on different monomers.