Time-Dependent Properties of Liquid Water: A

Comparison of Car-Parrinello and Born-Oppenheimer
Molecular Dynamics Simulations

I-Feng W. Kuo,† Christopher J. Mundy,† Matthew J. McGrath,‡ and J. Ilja Siepmann*.‡
Chemistry and Materials Science Directorate, Lawrence LiVermore National
Laboratory, LiVermore, California 94550, and Departments of Chemistry and of
Chemical Engineering and Material Science, UniVersity of Minnesota, 207 Pleasant
Street SE, Minneapolis, Minnesota 55455-0431
Received June 5, 2006

Abstract: A series of 30 ps first principles molecular dynamics simulations in the microcanonical
ensemble were carried out to investigate transport and vibrational properties of liquid water. To
allow for sufficient sampling, the thermodynamic constraints were set to an elevated temperature
of around 423 K and a density of 0.71 g cm-3 corresponding to the saturated liquid density for
the Becke-Lee-Yang-Parr (BLYP) representation of water. Four simulations using the Car-
Parrinello molecular dynamics (CPMD) technique with varying values of the fictitious electronic
mass (µ) and two simulations using the Born-Oppenheimer molecular dynamics (BOMD)
technique are analyzed to yield structural and dynamical information. At the selected state point,
the simulations are found to exhibit nonglassy dynamics and yield consistent results for the
liquid structure and the self-diffusion coefficient, although the statistical uncertainties in the latter
quantity are quite large. Consequently, it can be said that the CPMD and BOMD methods produce
equivalent results for these properties on the time scales reported here. However, it was found
that the choice of µ affects the frequency spectrum of the intramolecular modes, shifting them
slightly to regions of lower frequency. Using a value of µ ) 400 au results in a significant drift
in the electronic kinetic energy of the system over the course of 30 ps and a downward drift in
the ionic temperature. Therefore, for long trajectories at elevated temperatures, lower values of
this parameter are recommended for CPMD simulations of water.

Introduction some of water’s physical (e.g. a large dipole moment and
Water’s ubiquity on Earth leads to a vital role in most large polarizability) and chemical (such as self-dissociation)
biological and environmental processes, either directly or properties have made it difficult to use an empirical force
indirectly. As a result, water has been studied by experi- field to accurately reproduce experimental data over a wide
mental, theoretical, and computational methods for many range of state points.
years. However, water deviates in many important ways from The advent of the Car-Parrinello (CP) method in 19854
simple fluids to the extent of becoming a grand challenge enabled one to use a quantum mechanical description of the
for both liquid state theory and molecular simulation.1,2 electronic degrees of freedom combined with a classical
Originally, particle-based simulations employed empirical phase space trajectory involving a fictitious electronic mass
potentials for the determination of energies and forces,3 but parameter. The first CP molecular dynamics simulation for
liquid water followed in 1993,5 a significant advance despite
* Corresponding author e-mail: siepmann@chem.umn.edu. that computational resources limited this simulation to 32
† Lawrence Livermore National Laboratory. molecules and less than 4 ps for the combined equilibration
‡ University of Minnesota. and production periods. Since then, the increase in available
10.1021/ct6001913 CCC: $33.50 © xxxx American Chemical Society
Published on Web 07/27/2006 PAGE EST: 7.8

Two simulations were run to explore this issue more thoroughly by using a range of using this method (quenching the energy to 10-7 Hartrees) fictitious mass parameters for CP molecular dynamics in order to provide another level of comparison. CP method has now been applied to many aqueous systems the Kohn-Sham formulation of density functional theory22 at a variety of conditions (for examples.4 ps due to the kinetic energy term into the Lagrangian to efficiently kinetic energy of the fictitious electronic degrees of freedom propagate the electronic density (i. it is not certain whether All runs using the Car-Parrinello method are labeled CP- transport properties are sensitive to this parameter as long µ. These runs simulations and comparing the results to BO simulations that are labeled BO-1 and BO-2.18 which corresponds to a supercell of L ) 13. and.16. and 300 au) were explored. In particular. production periods were run liquid density for water calculated previously18 for the in the microcanonical (NVE) ensemble for 30 ps over which Becke-Lee-Yang-Parr (BLYP) exchange and correlation all reported properties were computed (unless otherwise functionals. This can for 64 water molecules. the first principles simulation protocols em. This adiabaticity breakdown results in CP Simulation Methods and Details forces on the ions becoming significantly different than the A series of six ab initio molecular dynamics (MD) simula. increasing ration taken from the middle of BO-1 and rescaling the the average velocity of the molecules (i. lowering the density).12.14 The goal of this work is to imer (BO) and CP molecular dynamics for time-dependent examine the effect of this parameter on dynamic properties properties of liquid water has been lacking. or lowering the barrier for diffusive transport equilibration period of about 5 ps in the canonical (NVT) (i. 16. the nuclear kinetic temperature of this study was a random initial velocity distribution to ensure divergence raised to 423 K.26 in consistent structural properties.e.4. 200.12-14 The effect of the The use of the CP method implies that a value of the fictitious electronic mass on dynamical properties (such as fictitious electronic mass parameter must be selected.17. Given the expense of ab initio ensemble was used to equilibrate each system and provide simulations. and the density was set to the saturated of trajectories.B J. which leads to the suffer from some degree of nonadiabaticity between the conclusion that not all dynamical properties are affected nuclear and electronic degrees of freedom. i. see refs 6-10). The CPMD program is also capable of quenching the as reasonable values are used (which may or may not electronic density after every time step instead of propagating coincide with the upper range suggested by previous works it with the CP method.27 tions was performed using the publicly available software More quantitative results for the system of interest (water) suite CPMD. The time steps vary between runs (from 0. conserving Martins-Troullier pseudopotentials23 with Klein- Recently. An temperature). In this work. which necessarily impacts the trajectory.e. were taken from the saturated liquid phase of an equilibrated The main thermophysical quantity in question is the self. three additional choices of the is clear evidence that vibrational properties are affected by fictitious mass (µ ) 100. many molecular diameters.20 advanced our understanding of the physical and chemical The choice of these functionals as well as the norm- properties of aqueous systems.27 which is equally by the change in fictitious electronic mass. Subsequently. a value of µ ) 400 au appears but a comprehensive comparison between Born-Oppenhe.11-15 It has been suggested that the appropriate of 85 Ry for the Kohn-Sham orbitals follow those used in selection of the fictitious electronic mass parameter will result previous CPMD simulations. which clearly demonstrates .. To precisely compute this quantity the and scaled to the computed average density of F ) 0.19. quench the electronic density at every step to a given The initial configurations for all simulations except BO-2 tolerance.9176 Å starting positions. Theory Comput. diameters from their origin for each 30 ps trajectory. simulation in the microcanonical ensemble of 64 molecules rinello. man-Bylander transformation to the fully nonlocal form24 ployed in studies of liquid water have been examined to describe the core electronic states and a plane wave cutoff critically.25. This is accompanied by an ionic schemes used feasible). Chem.14. computing power and the refinement of algorithms has led functional theory to provide a quantum mechanical descrip- to an increased ability to perform these simulations.13 and a duration of 20 ps or less. Monte Carlo simulation at T ) 423 K in the Gibbs ensemble diffusion coefficient. Kuo et al.484 fs) and are reported in Table 1. therefore. to be a reasonable choice. A rigorous statistical analysis is presented in an attempt to Results and Discussion determine the nature and magnitude of inconsistencies for It is well-known that all simulations utilizing the CP method both dynamical and structural properties.4 The CP approach introduces a fictitious electronic and µ ) 800 au being terminated after 4. it makes the integration drifting by around 0. Although there of water. It is the goal of this study the Born-Oppenheimer surface.0484 to to move on average between four and five molecular 0. the fictitious mass parameter. The is used with the gradient corrected exchange functional of information obtained from these studies has substantially Becke19 and the Lee-Yang-Parr correlation functional.21 Four of these simulations were based on the are shown in refs 12 and 14.71 g molecules must move a significant distance from their cm-3.e. BO forces. ref 14 shows a extended Lagrangian approach developed by Car and Par.20 This enabled the molecules in the simulation stated).17.17 and liquid water. For diffusion constant and vibrational frequencies) has been previous simulations of liquid water near ambient conditions examined for both crystalline systems16. This allows one to use density temperature drop of around 30 K. This leads to direct sampling from for consistent structural properties). and the tion of the electronic component of the system.e.05 au. raising the velocities to generate a slightly higher temperature. BO-2 was started from a configu- be achieved by increasing the simulation length. an effect that grows with increasing values of the fictitious electronic mass.

and no to water with significantly less structure than observed here results are shown for this run. the self-diffusion coef- to remove spurious thermostating effects from dynamic ficient was computed from the Einstein relation properties.06) 8. with µ ) 400 au) shows a with the (low-temperature) BO-1 simulation showing slightly drift over the full 30 ps that is comparable to the drift for more structural ordering.14(0. presumably because Figure 1.20(0. CP-300.37(0.7) 8.484 417(5) 2.24 393(n/a) 3. dot). 7b D7.073 418(10) 2.07 399(n/a) 2. electronic kinetic energy. of equal length (i.0 BO-SGGGc 0.10) 12.0 g cm-3) at that control of the electronic degree of freedom through the elevated temperature (≈400 K) yield significantly more use of thermostats can prevent drifting of the fictitious structure. with the numbers in parentheses being the 95% confidence interval Figure 2. It has been shown previously and that simulations of dense water13 (F ) 1. CP-200. C Table 1. which is reasonable when compared to previous studies. Errors are estimated by breaking the full trajectories into three blocks where the slope is found from a linear least-squares analysis . Again. CP-200 (red.17 the nonadiabaticity of the system. Simulation Details (Fictitious Mass and Time Step) and Selected Results (Average Nuclear Kinetic Temperature.484 426(5) 2.5) 12.g. The instantaneous fictitious electronic kinetic these error limits are most likely underestimated (see below).3(6.14.7 and D7.9 CP-300 300 0.15) 12.7 g cm-3) and much higher temperatures (653 K) lead microcanonical ensemble cannot be recommended. Despite this. tematic fictitious mass effect.12) 12. dot). and consequently the confidence intervals reported in Table 1 are probably underestimated. we note that simula- Consequently. From top to bottom: CP. Tangney. the structural properties are fairly consistent.13 for descriptions) the following: BO-1 (black.23. The oxygen-oxygen radial distribution functions assuming a normal distribution.3) 14. using a fictitious electronic mass of 400 au tions of supercritical water29. The lines correspond to (refer to text carried out by Schwegler et al.71 g cm-3. 27b µ δt Tnuc (10-5 (10-5 run (au) (fs) (K) gOO(rmax) cm2 s-1) cm2 s-1) BO-1 0. b D2. Height of the First Peak in the Oxygen-Oxygen Radial Distribution Function and Diffusion Coefficient) for the Car-Parrinello (CP) and Born-Oppenheimer (BO) Molecular Dynamics Simulationsa D2. Additional analysis (see below) indicates that the resulting block length of 10 ps is shorter than the correlation time for the system.30 carried out at a similar density for long simulations of water at elevated temperature in the (≈0..2(n/a) CP-SGGGc 340 0. It can be seen from this table that the average nuclear kinetic temperatures range from 417 K (for BO-1) to 428 K (for CP-100). Figure 1 shows the The oxygen-oxygen and oxygen-hydrogen radial dis- electronic kinetic energy of all four CP simulations reported tribution functions are depicted in Figures 2 and 3.6) 9. and CP-300 (blue.048 422(6) 2.5(3.60(n/a) 2. showing a spread in the first peak height of the oxygen-oxygen radial distribution function of 0. as discussed recently by 400. solid). 10 ps). and calculating the 95% confidence interval assum- ing a normal distribution.04) 12. principles simulations of liquid water. It should be noted that one of the agreement between the five simulations is quite good but reported simulations (CP-400.20(0. solid).28 but caution needs to be applied To compare transport properties. and CP-100. it should be noted that the 95% confidence limits for BO-1 and CP-300 do not overlap.3(2.28(0.0 BO-2 0.10(n/a) 1.r(0)|2〉 (1) 3 properties computed for the current simulations. e.3 CP-100 100 0. c CP-SGGG and BO-SGGG are simulations for the PBE functional K and F ) 0.8(5. BO-2 (red.Time-Dependent Properties of Liquid Water J. 1 Table 1 gives a summary of structural and transport 2tD ) 〈|r(t) . Theory Comput. Chem. In comparison to other first the 4.4(6.11-14 However. here as a function of time. respectively.4 ps trajectory with µ ) 800 au from ref 14.e. computing the property of interest.7 CP-200 200 0. CP-100 (black.2(n/a) a The values reported are the averages of three 10 ps blocks.27 denote diffusion obtained from molecular dynamics simulation of water using coefficients calculated for the 2-7 ps region of the three blocks and the BLYP exchange/correlation energy functional at T ) 423 for the 7 to 27 ps region of the full production period. energy as a function of time for all four Car-Parrinello Another possible explanation might be some type of sys- molecular dynamics simulations.048 428(7) 2.4) 12. dot).

The oxygen-hydrogen radial distribution functions Figure 5.71 g cm-3. seven time origins are used for each of the 10 ps surrounding solvation shell).13 for BO and CP period.0-7. CP- 200 (open square). The mean squared displacements obtained from be considered when comparing diffusion properties. A comparison 1.5 higher barrier for diffusive transport (escape from the ps. The runs are as follows: BO-1 (solid circle). The self-diffusion coefficients for all five simulations self-diffusion coefficient. we have also peak height and self-diffusion coefficient. The line styles and colors are the the simulations into three parts of equal length and computing same as Figure 2. runs are at a different state point (slightly lower temperature .. To improve statistics.D J. Figure 5 shows a plot of the self- show overlapping confidence limits and range from 8. the values for these segments. but there does exchange/correlation energy functional at T ) 423 K and F ) not appear to be any strong relation between the temperature 0. the BLYP representation appears to yield a liquid phase with sluggish diffusive properties. Because these ties (see Table 1). In addition. Movement in a more structured fluid results in a (MSD). Figure 3. one must consider how the transient changes in structure affect to fit the 2. i.e. the self-diffusion coefficient of water changes by almost a factor of 2 for a temperature change of 20 K at lower temperatures. The line styles and colors are the same as Figure and diffusion coefficient. Theory Comput. Assuming that the experimental correlation of high- temperature self-diffusion coefficients given in eq 4 of ref 31 can be extended to the state point investigated here (which would be inside the two-phase loop for real water). one obtains a self-diffusion coefficient of 31. origins were taken every 0. Kuo et al.8 × 10-5 cm2 s-1 (for CP-100). The molecular dynamics simulation of water using the BLYP spread of temperatures reported here is 11 K. Data points were obtained by dividing K and F ) 0. Using an unweighted least-squares method to fit a straight of the MSD for the five simulations (see Figure 4) shows line to these points gives a correlation coefficient of -0. whereas it yields a vapor-liquid coexistence curve that is shifted downward. Chem. which is approximately a factor of 3 higher than the values observed here. influence the simulation more. Ernzerhof exchange/correlation functional. The diffusion coefficient as a function of the peak obtained from molecular dynamics simulation of water using height of the first maximum in the oxygen-oxygen radial the BLYP exchange/correlation energy functional at T ) 423 distribution function.3 (for diffusion coefficient as a function of the height of the first BO-1) to 12.71 g cm-3. computed the diffusion coefficient from a least-squares Table 1 also includes self-diffusion coefficients and peak analysis fit to the 7-27 ps region of the full production heights reported by Schwegler et al. BO-2 (solid square). which in turn produces a slower blocks. suggesting that other factors may 2. graphically the large but statistically insignificant deviations indicating a moderately negative linear correlation between between the five simulations.0 ps region of the mean square displacement diffusion.18 Experimentally. and CP-300 (open triangle up). CP-100 (open circle).32 and consequently the varying temperatures present in microcanonical simulations should Figure 4. The results obtained for this longer time interval agree molecular dynamics simulations using the Perdew-Burke- with the 10 ps block averages to within statistical uncertain. suggesting that peak in the oxygen-oxygen radial distribution function for reasonable values of µ with regards to structural properties all 15 10-ps blocks used in the statistical analysis in Table also produce consistent diffusion coefficients.8 × 10-5 cm2 s-1. Thus.80. For instance.

The difference in the reported height of the first signal poorly equilibrated samples). Unfortunately the self-diffusion constant (being the one should be very cautious in comparing the transport long-time limit of the Einstein relation) is not obtainable from properties of simulations with significant differences in an instantaneous snapshot or even a short time interval. Thus. fewer escapes from the solvation shell) than 50% higher or lower than the mean value. The symbols are the same as in Figure 5. and the two complete fluctuations. oxygen radial distribution function and of the self-diffusion It has been found that under some conditions. Although the magnitude of the fluctuations in the as above. The figure also depicts the same difference in self-diffusion coefficient is around a factor of trend as is seen in Figure 5. Data points are given for properties computed over the but significantly higher density) and use a different func. It is evident that the peak of the oxygen-oxygen radial distribution function correlation times for these systems are on a scale approaching between CP and BO runs performed by Schwegler et al. they were run only for 20 ps and yield substantially lower Specifically. an attempt can be made of the system.Time-Dependent Properties of Liquid Water J.. previous 10 ps. However. Therefore time is a worthwhile exercise in several respects. By using a linear-least-squares analysis and fitting a line liquid-phase yields a smaller self-diffusion coefficient as well to the data in Figure 5. we determined this value here over the 2. tional.0 structure is small (and might therefore be overlooked). the ps range of 10 ps blocks but repeat this procedure for multiple correlation times are very long.e. structure.34 Although the MSDs an Einstein plot of the full 10 ps. no value of the peak height differs from the self-diffusion coefficients (presumably because of the higher average by more than 10%. near the simulation length since no system undergoes more than the same nuclear kinetic temperature (400 K) is 0.0 simulations.5 (which includes the range of values found here and Figure 7 graphically illustrates another interesting feature over which the data appears to be linear). providing in Figure 6 with the respective average value calculated from evidence that the reported difference in ref 13 could be all five simulations is plotted as a function of time.e. and correlate. viewed with caution.6 and 3. average value across all simulations as a function of time. The ratio of the 10 ps interval values change of diffusion coefficient of a factor of 3. water coefficient as a function of simulation time with the former described by certain density functionals may exist in a glassy averaged over the previous 10 ps and the latter obtained from state even at elevated temperatures. but it still provides insight into the evolution tests were carried out to ensure that water under these . namely that a more structured 2. E Figure 6. Chem. two its neighbors). i.5.1). Data points are given for Figure 7. This produces data points from this work (see Figure 4) appear to be quite linear (and that are necessarily correlated (each point overlaps 90% with there is no indication that they would reach a plateau).0-7. the trajectories reached much smaller MSDs of the instantaneous mean-square-displacement are found (and. This results in a of these simulations. to 2. an estimation of the initial times along the trajectory to follow the evolution. Furthermore. hence. some values density). they cannot be compared directly to the simulations performed in this work. Theory Comput. one can compute the expected as showing significant overlap between the BO and CP diffusion coefficients for a change in peak height from 2. It can give small uncertainties in the structure of a simulation can lead information on the extent to which properties fluctuate and to even larger uncertainties in the diffusion coefficient. i. Evolution of the peak height of the first maximum in the oxygen-oxygen radial distribution function (top) and of the diffusion coefficient (bottom). because height of the oxygen-oxygen radial distribution function.33. The ratio of the instantaneous peak height (filled the peak height and diffusion coefficient calculated over the circles) and self-diffusion coefficient (open triangles) to the previous 10 ps. It appears that for all five simulations these to explain the reported difference using insight acquired from two properties undergo fluctuations (versus a drift that would this work. Lines are drawn as guides for the eye. These largely due to the difference in structure (peak heights of results demonstrate that the fluctuations of the self-diffusion 2.. This is also those reported here. statistical uncertainties from block averages needs to be Figure 6 shows a plot of the first maximum in the oxygen. demonstrated in Table 1 by the much larger confidence Looking at the evolution of the system’s properties over intervals attached to the self-diffusion coefficient. one might expect larger statistical coefficient are significantly greater than that of the first peak uncertainties for the simulations by Schwegler et al. On the other hand.

if the molecular distances adopt a obtained here for the librational and stretching modes (shown Gaussian distribution. and stretching modes) given by for clarity. Figure 8 shows plots of both method.37 The spectrum is divided into three regions (from top conditions is truly in a liquid state.38-40 and further validates the use of a scaling generate large jumps in β. resolvent transform of the total velocity autocorrelation func- tion. fictitious mass. power spectra computed by integrating from an arbitrary just like for β and the MSD. so motion is not completely random. Chem. Origins taken every 0. These median peak positions and R2 is not anticipated to be zero. The plot of R2 as a function of time span was covered in the trajectories. Figure 8. Because β is a can be represented by a sum of sinusoids. One expects this parameter to tend The peak “position” is not well defined for the broad peaks to zero at long times.17. As for the MSDs. Kuo et al. is to bottom: librations. Poor statistics after this time lead to power spectra than the CP simulations despite that an equal fluctuations around unity. time is a little less clear. The resulting derivative.r(0)|2〉) of the total velocity autocorrelation function could not β(t) ) (3) d ln(t) adequately resolve all low-frequency modes (less than 1000 cm-1) of these systems.35 The second Dynamical information of water interacting with its local indicator of diffusive dynamics. but then it begins to diverge Table 2 lists the median values of each peak in the RRT again. RRT is also a direct transform of the these indicators over the full trajectories for all five simula- data from the time domain into the frequency domain and is tions. R2 hovers around in the top and bottom panels of Figure 9). so 0.ln(t .36. The effect of the electronic mass parameter The indicator β(t). this can be explained by poor statistics. Power spectra computed from the regularized colors are the same as Figure 2. these indicators were computed using exactly equivalent to discrete FT when the frequency spectra multiple origins spaced 0. A combination of Figures show a systematic red-shift for the bending and stretching 4 and 8 leads to the conclusion that water represented by modes in the CP trajectories. Consequently. same value on the other side.5) mid-infrared region do show signs of dynamic retardation (4) due to larger masses.r(0)|4〉 R2(t) ) -1 (2) 3〈|r(t) . the power spectra were A value of unity for this parameter indicates that the system generated with the regularized resolvent transform (RRT) is diffusing in a liquid regime. R2. The line styles and colors are the same as Figure 2.5) . It was found here that the Fourier transform (FT) d ln(〈|r(t) .r(0)|2〉) . Therefore.05 ps did parameter when analyzing the mid-infrared region to ex- not give qualitatively different results. The to these origins (examination of Figure 4 reveals disconti- regions shown correspond to the molecular librations. zero for intermediate times. For short times the configura.F J. is equal to unity on the librational modes of water is less clear. Consequently.r(0)|2〉) β(t) ) significant fictitious mass effects. 〈|r(t) . β. intensity value (close to zero) on one side of the peak to the tions are still correlated. Theory Comput. as shown in Figure 8. and the O-H stretching modes. For all simulations. The values of the R2 (top) and β (bottom) parameters as a test of glassy diffusion.0. this indicator would be artificially altered close spectra are shown in the three sections of Figure 9.37 Like FT. At long times. and decays to zero for random walk statistics.ln(〈|r(t .0. The line styles and Figure 9.36.5 ps is used here trapolate the frequency to the limit of an infinitely small for consistency.71 g cm-3. This is in agreement with previous With this finite-difference method the discontinuities do not works16. bending motion.5 ps apart. the nuities here). The first indicator. Whereas the self-diffusion coefficient shows no statistically ln (〈|r(t + 0.5) .r(0)|2〉2 the BLYP exchange/correlation functional is not glassy at T ) 423 K and F ) 0. with the magnitude of the shift . is given by environment can be gleaned from the vibrational power spectrum. the power spectra in the ln(t + 0. it was decided to compute H-O-H bending motion. It should also for all five runs in the region of good statistics (time scales be noted that the BO trajectories appear to yield “smoother” up to about 15 ps).5) .

41 The most likely explanation governed directly by the instantaneous forces and the reduced is that the tetrahedral hydrogen-bonded network is very mass of a given normal mode. The evident. This explanation is that depend on free energies (e. This agreement lends credence to the belief that the mass parameters there will be a much longer time scale over differences seen in the CP simulations are not artifacts of which this increase will lead to a noticeable decrease of the the analysis procedure and reaffirms conclusions from earlier ionic temperature. Again. The emphasized that even the CP trajectories with µ ) 100 or variations between the two spectra are minimal. values that do not under the auspices of the U. has allowed us to look at the Maginn for many helpful discussions and Larry Fried and structural and transport properties of water using density Charlie Westbrook for their ongoing support of this work. Part of this work was performed reasonable values of µ (in other words. low-density conditions point out that the instantaneous forces of CP simulations with investigated here. All Financial support from the National Science Foundation five simulations show similar structural properties with a Grants CTS-0138393 and ITR-0428774. shift values).S. Median Locations for the Three Vibrational on the simulation time scales used here there does not appear Modes (in units of cm-1) to be a statistically significant difference in transport proper- run libration bend stretch ties between BO and CP molecular dynamics simulations BO-1 551 1617 3522 as long as reasonable values of µ are used. for these fictitious 2-4. Thus.). The median values for the librational magnitude estimates for transport properties are reliable using peak of the CP simulations show a red-shift when compared current technology and algorithms for first principles simula- to the BO runs. µ. Thus. a 3M Foundation range in the height of the first peak in the oxygen-oxygen Graduate Fellowship (M.12. Computer resources All five simulations show large fluctuations and hence were provided by LLNL Computing and the Minnesota large uncertainties for the self-diffusion coefficient. it should be is the close agreement obtained for both BO runs.S.2. a concern supported by the short simulation of the fictitious mass parameter.I. However.M. Consequently. interchange between different local any value of the electronic mass are different than the BO configurations is fast. even for small values of this parameter.g.16. statistically significant differences in structural properties on J. diffusive transport) should be significantly less affected given a reasonable choice of µ Conclusions because instantaneous differences in the forces can cancel A series of long molecular dynamics trajectories for liquid upon averaging. suggests large uncertainties in the low-frequency region of From this it can be concluded that. and their lifetimes are too short to forces for an identical system. It has been Computational Science Graduate Fellowship (M. thank the University Relations Program the observed simulation time scales.J. work that certain properties (in particular. despite the 200 au show a small increase of the fictitious electronic difference in structure and diffusivity highlighted in Figures energy over the 30 ps trajectory. On the other hand. functional theory with BLYP exchange and correlation. properties establish specific librational features. and 27 fluctuational at the high-temperature. . and a Department of Energy radial distribution function of about 0.17.Time-Dependent Properties of Liquid Water J. Chem. but not systematic. If one assumes BO-2 553 1617 3525 that the statistical uncertainties for the self-diffusion coef- CP-100 498 1605 3491 ficient are solely a function of the distance a molecule travels CP-200 495 1599 3455 on average. those directly One observable that is clearly influenced by the choice of related to forces and momentum via changes of the mass) µ is the power spectrum.g.) are concluded before. the radial distribution supported by recent experimental analysis of vibrational function) or are governed by long-time processes involving lifetimes in liquid water. water near 423 K obtained from BO molecular dynamics and CP molecular dynamics with varying values of the Acknowledgment. We thank Juerg Hutter and Ed fictitious mass parameters. but increasing the magnitude of the fictitious tions at ambient conditions (with the use of higher temper- electronic mass does not necessarily lead to a further shift atures and lower densities enabling somewhat more precise in the peak position. several physical properties length but obfuscated by the agreement between the BO (including structural information and the self-diffusion coef- simulations (see below).M. References 16. Supercomputing Institute. A spectrum observed here does not show the distinct features likely explanation for the manifestation of fictitious mass observed in CP molecular dynamics simulations for the water effects in the power spectrum is that this observable is spectrum at ambient conditions. 17. one should note that the librational part of the lower frequency. Department of Energy by the lead to a large drift in the electronic kinetic energy and a University of California Lawrence Livermore National subsequent lowering of ionic temperature) do not produce Laboratory (LLNL) under contract No.42 free energy barriers (e.14 and shall be reiterated here. simulations near ambient temperature and density CP-300 529 1595 3446 would require around 500 ps to obtain a diffusion coefficient with the same statistical uncertainty (about 50%) as found relative to the BO value being smallest for CP-100 and in this work. G Table 2. that gratefully acknowledged. Theory Comput. W-7405-Eng-48.. (LLNL) for hosting their sabbatical visit.27 fictitious electronic mass shifts the spectrum into regions of Finally. ficient) of CP and BO simulations are indistinguishable on One striking feature present in both Figure 9 and Table 2 time scales of tens of picoseconds.J. for reasonable values the spectra. and M.M.J. it appears that only order of largest for CP-300. in which using CP dynamics with are influenced by the use of the CP method.

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