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22 February 2000

Extrapolation and perturbation schemes for accelerating the

convergence of quantum mechanical free energy calculations via the

Fourier path-integral Monte Carlo method

Steven L. Mielke

Mail Stop K8-91, Richland, Washington 99352

Jay Srinivasan and Donald G. Truhlar

Department of Chemistry, Chemical Physics Program, and Supercomputer Institute,

University of Minnesota, Minneapolis, Minnesota 55455-0431

We present two simple but effective techniques designed to improve the rate of

convergence of the Fourier path-integral Monte Carlo method for quantum partition

functions with respect to the Fourier space expansion length, K, especially at low

temperatures. The first method treats the high Fourier components as a perturbation, and

the second method involves an extrapolation of the partition function (or perturbative

correction to the partition function) with respect to the parameter K. We perform a

sequence of calculations at several values of K such that the statistical errors for the set of

results are correlated, and this permits extremely accurate extrapolations. We

demonstrate the high accuracy and efficiency of these new approaches by computing

partition functions for H

2

O from 296 K to 4000 K and comparing to the accurate results

of Partridge and Schwenke.

________________

MD 21218

2

I. INTRODUCTION

Fourier path integral methods

1-14

, especially when coupled with Monte Carlo

integration, provide an efficient means of calculating accurate quantal partition

functionsand hence absolute free energieswithout diagonalization of molecular

Hamiltonians. Thus these methods become increasingly attractive as the system size

increases and diagonalization becomes prohibitively expensive. Unfortunately, Fourier

path integral methods suffer from slow convergence with respect to the maximum

number, K, of Fourier coefficients used in the expansion of the paths. The canonical FPI

method is known to converge as O(1/K).

15

By using the technique of partial averaging

6,7

the convergence rate may be increased to O(1/K

2

).

15

Unfortunately, efficient use of this

technique requires that the potential function have an analytic Gaussian

transformwhich most molecular potential energy functions do not possessor that the

potential be expanded in a Taylor series. The latter approach, known as gradient partial

averaging,

6,7

requires the calculation of the diagonal elements of the Hessian which can

be very expensive in many important cases, especially for systems of large

dimensionality. Additionally, considerable human labor may be involved in coding the

Hessian for a desired potential. In the present paper we introduce two simple, yet highly

effective, techniques for ameliorating the costliness of the slow convergence of FPI

methods with respect to K. Both of these techniques can also be applied in the partial

averaging approach.

We illustrate the new techniques by using them in calculations of the absolute free

energy of water vapor over a temperature range of a factor of 13.5.

3

II. THEORY

II. A. Algorithm overview

We begin by reviewing basic theory and the algorithmic implementation of the

FPIMC method as we have used it.

10-12,14

The partition function for a system with

spinless nuclei may be obtained by calculating the trace of the canonical density operator,

i.e.,

Q T d ( ) ( , ; )

x x x (1)

where is a symmetry number equal to N

i

i

!

where N

i

is the number of atoms with a

given atomic weight,

16

x is an N-dimensional point in mass-scaled Jacobi coordinates,

is 1/k

B

T, where k

B

is Boltzmann's constant,

( , ; ) exp( ) x x x x H (2)

is the coordinate representation of the density operator, and H is the Hamiltonian

operator. Elements of the density operator may be expressed as path integrals

1,2

( , ; ) ( )exp [ ( )] x x x x

x

x

D s dsH s

1

0

h

h

(3)

where h is Planck's constant divided by 2 and

Dx

x

x

( ) s

paths parameterized by s and beginning at x and ending at x.

After substituting Eq. (3) with x = x into Eq. (1), expanding the paths in a Fourier

series,

4

x s x a

k s

j j jk

k

K

( ) sin +

j

(

,

\

,

(

h

(4)

where K is the length of the Fourier expansion, and simplifying, we obtain the expression

Q T

J T

dx da

a

S

j

j

N

jk

k

K

j

N

jk

jk

k

K

j

N

( )

( )

exp ( , )

j

(

,

,

\

,

(

(

j

(

,

,

\

,

(

(

j

(

,

,

\

,

(

(

L

1 1 1

2

2

1 1

2

x a . (5)

In this equation,

jk

k

2

2

2 2

2

h

, (6)

where is the scaling mass of the mass-scaled Jacobi coordinates, S( , ) x a is the action

integral for a given path and is calculated by

S dsV s ( , ) [ ( )] x a x

0

h

(7)

where V(x) is the potential energy, and J(T) is the Jacobian of the transformation from the

integral over paths to the integral over Fourier coefficients and is given by

J T

j

N

jk

k

K

( )

2

1

2

1 1

h

. (8)

We put Eq. (5) into a form appropriate for Monte Carlo integration by multiplying

and dividing by the free particle partition function and restricting the configuration space

to a finite domain D. This yields

5

Q T

Q T

d d

a

S

d d

a

K

jk

jk

k

K

j

N

D

jk

jk

k

K

j

N

D

[ ]

( )

( )

exp exp ( , )

exp

j

(

,

,

\

,

(

(

[ ]

j

(

,

,

\

,

(

(

j

(

,

,

\

,

(

(

fp

x a x a

x a

2

2

1 1

2

2

1 1

2

2

, (9)

where

Q T V

D

j

N

fp

( )

/

j

(

,

\

,

(

2

2

1 2

1

h

(10)

and V

D

is the volume of the domain D. We choose V

D

to be a hyperannulus defined by

l u

where the hyperradius is defined by

x

j

j

N

2

1

. (11)

To improve the efficiency of the calculation we subdivide V

D

into several concentric

hyperannulii and sample these via an adaptively optimized stratified sampling scheme.

We also employ importance sampling in the configuration space, and we have

implemented a number of screening schemes to eliminate the work associated with

evaluating contributions from paths that have a negligible contribution. The discussion

of the new methods we present below does not require a detailed understanding of these

numerical issues so we refer the reader to previously published papers

10-12,14

for further

details.

Partition functions calculated with Eq. (9) include contributions from dissociated

species. These contributions are formally divergent as they scale linearly with the

volume of the system. (This problem is not unique to the FPI method; it always occurs

when one calculates free energies of bound species by using configuration integrals

6

without making the harmonic oscillator approximation.

17,18

) At high temperatures or for

weakly bound systems, the treatment of dissociated species must be carefully defined. In

the present study we wish to compare our results to partition functions obtained from

bound-state eigenvalue calculations; thus we wish to remove the contributions from

species with energies greater than the dissociation energy. This can be done by

neglecting contributions from all paths for which the energy of the configuration space

sample point, x, is above the energy needed for dissociation. (Note that other points on

the path are allowed to have energies above the dissociation limit.) Since it is not

convenient to include the kinetic energy in this criterion, we instead neglect contributions

from paths where the potential energy at x is above the dissociation limit. This removes

nearly all of the effects from dissociated species without excessive cost.

II. B. Perturbative corrections

Partition functions calculated via the FPIMC method converge asymptotically as

O(1/K). This slow convergence rate means that well converged results require large

Fourier expansion lengths, K. It is thus useful to consider the high-k elements of the

Fourier expansion as being a perturbation of the low-K result. The identity

Q T Q T Q T

K K K K [ ] [ ] , ,

( ) ( ) ( ) +

corr

, (12)

where

Q T Q T Q T

K K K K corr, , [ ] [ ]

( ) ( ) ( )

(13)

with K < K, forms the basis for our approach. The first term on the right hand side of

Eq. (12) is large in magnitude but may be affordably calculated, the second term on the

right hand side of Eq. (12) is expensive to calculate but small in magnitude (for

7

sufficiently large K ). Equation (12) will be useful if we can devise a Monte Carlo

integration scheme such that we need to calculate substantially fewer samples of the

expensive Q

corr,K,K

(T) term to achieve a given level of accuracy in Q

[K]

(T) than we

would need if we calculated Q

[K]

(T) directly. If, for instance, Q

[K ]

(T) is converged to

within 10% with respect to the Fourier space size, only 1% of the total number of

samples is needed for Q

corr,K,K

(T) in order to obtain comparable statistical errors for the

two terms.

In order to calculate Q

corr,K,K

(T), we perform simultaneous calculations for K

and K . For each Monte Carlo sample we form two paths from a single set of random

Fourier coefficients. Thus both paths begin and end at the same configuration space

sample point, x, and the first K Fourier coefficients of the higher order path are identical

to those of the lower order path. We accumulate statistics on Q

[K]

(T), Q

[K]

(T), and

Q

corr,K,K

(T) in a single run. Except for statistical errors, the perturbative correction is

calculated exactly by this treatment. We then calculate Q

[K ]

(T) using a substantially

larger number of samples than we use for the Q

corr,K,K

(T) run. We can calculate the

variance of our final result via

var[ ( )] var[ ( )] var[ ( )]

[ ] [ ] ,

Q T Q T Q T

K K K

+

corr

. (14)

The standard deviation, , in any quantity is taken (as usual) as

var/ N (15)

where N is the number of samples used to evaluate the given quantity.

We actually have two calculations of Q

[K ]

(T) from the procedure above, one

using a large number of samples and a less accurate result obtained concomitantly with

the calculation of Q

corr,K,K

(T); when necessary, we will distinguish these two results

8

with superscripts of L and S respectively to denote "large" and "small" samples. The

statistical errors in Q

corr,K,K

(T) and Q

[K ],S

(T) are highly correlated so we can obtain a

correction term of significantly greater accuracy via

( )

( )

( )

( )

, ,

[ ],

[ ],

, ,

Q T

Q T

Q T

Q T

corr K K

K

K

K K

L

S

corr

. (16)

It is difficult to precisely estimate the degree of improvement we obtain by Eq. (16) so

when we quote statistical error bars, we will use the conservative estimate of Eq. (14).

II. C. Extrapolation with respect to K

In the absence of statistical error, the partition function tends to converge

smoothly and monotonically with respect to the size of the Fourier space. It is thus very

tempting to perform calculations for a few moderate values of K, and then extrapolate the

resultstaking advantage of the known asymptotic convergence rateto the K = limit.

The one difficulty with this approach is that the statistical errors for the various

calculations limit the accuracy of the extrapolation procedure. We instead seek to form a

sequence of results that differ in K while having statistical errors that have a high

correlation. We proceed as above by calculating Q

[K]

(T) for several values of K

simultaneously where, for each sample point, all of the paths are determined using a

single common set of random Fourier coefficients. When calculated in this manner, the

sequence of results displays very regular convergence properties with respect to K even

when the statistical errors are very large. Even for a single sample point, results have a

very strong tendency to decrease monotonically with increasing K.

9

Calculating results simultaneously for several values of K in the manner

suggested above is also somewhat less expensive than performing independent

calculations. In general the sets of paths need not intersect except at x, which is not a

quadrature node when we use Gauss-Legendre quadrature. Thus we need the same

number of potential evaluations when doing simultaneous calculations as we would for

independent runs. However, all of the work required to select configuration space

samples (with a distribution governed by an arbitrary importance function) needs to be

done only once. Additionally we need to calculate only a single set of Gaussian random

numbers to sample the Fourier space. It would also be possible (using partitioned matrix

techniques) to save work during the formation of the paths provided that some quadrature

nodes are chosen the same for paths constructed with different values of K. If we sample

the configuration space much more frequently than we sample the Fourier space (i.e., if

we reuse the relative paths a large number of times) these possible savings are modest

since the potential evaluations usually dominate the computational cost. Thus we have

not chosen to exploit this option.

We can apply the extrapolation scheme not only to Q

[K]

(T) itself but also to the

perturbative corrections to Q

[K ]

(T). The relative error of each of the perturbative

corrections is approximately constant so we calculate the K = error bars via

( , , ) ( , , )

, ,

, ,

corr corr

corr

corr

K

Q

Q

K K

K

K K

. (17)

We can also refine the extrapolated correction using Eq. (16).

We perform calculations of Q

corr,K,K

(T) at three or more values of K, and we

extract Q

corr,,K

(T) by fitting to the functional form

10

Q T Q T

A

K

B

K

K K K corr corr , , , ,

( ) ( )

+ +

2

. (18)

II.D. Absolute Free Energies

Absolute internal free energies are obtained from the final partition functions by

G RT Q T ln ( ) (19)

and these may (if desired) be adjusted to any desired standard state by the addition of an

appropriate analytic contribution from overall translation.

III. CALCULATIONS AND DISCUSSION

We will demonstrate the effectiveness of the two new computational schemes on

partition function calculations of water. Water has been widely studied as a prototype for

vibrations in a polyatomic molecule.

19

For our purposes the best set of partition

functions obtained by eigenvalue summation for a given potential energy surface are

those of Partridge and Schwenke.

20

Therefore we have chosen to use their potential

surface and compare to their data. (Another recent calculation of water partition

functions via direct diagonalization has been presented by Harris et al.

21

)

For consistency with prior calculations we use nuclear (rather than atomic)

masses of 1836.152697 and 29148.94642 for H and O respectively. Partridge and

Schwenke

20

tabulate partition functions with a zero of energy set at the ground state

energy of E

0

= 4638.39 cm

1

(whereas we use the minimum of the potential as the zero

of energy) and they include a factor of 4 for nuclear spin effects (which we do not

include). We scale their results by a factor of exp(E

0

)/4 to compare with ours.

11

We performed calculations at ten temperatures in the range 296 K to 4000 K. For

each temperature we perform a calculation using a large number of samples and a modest

value of K (denoted K) using the parameters given in Table I. We then performed

calculations of Q

corr,K,K

(T) for several larger values of K using the parameters given in

Table II and extrapolated the results to the K = limit using Eq. (18). In both cases we

employed an importance function given by

f

R R R R R R

( ) exp x

j

(

,

\

,

(

j

(

,

\

,

(

j

(

,

\

,

(

,

,

,

]

]

]

]

HH HH

e

HH

OH OH

e

OH

OH OH

e

OH

2 2 2

(20)

where the R

XY

e

are taken to be the equilibrium atom-atom distances. The parameters we

used for the importance function of Eq. (20) are given in Table I. The width parameters

were roughly optimized at 4000 K and used without re-optimization at lower

temperatures. The variance reduction due to importance sampling is about a factor of

three at high temperature, but less at lower temperatures; however, the savings in

computer time are less than the naive estimate (which would be the square of the variance

reduction factor) because the screening options

14

are more effective when importance

sampling is not used. A more quantitative discussion of the efficiency savings afforded

by importance sampling is provided elsewhere.

14

Table III presents the results of the two sets of calculations at K = K. Tables IV

and V give the Q

corr,K,K

(T) calculations together with two different extrapolations to the

K = limit. Table VI compares the final FPIMC partition functions to the calculations

of Partridge and Schwenke.

20

Our partition function calculations contain errors from several sources. Statistical

error is likely to be the largest source of error. Our sampling is not entirely uncorrelated

12

since we reuse the same Fourier space samples with many configuration space samples

(100500 for the present set of calculations), but this is a rather short term correlation and

numerical tests

14

indicate that uncorrelated error estimates are accurate. Thus our

statistical error bars are calculated using formulas appropriate for uncorrelated sampling.

Our statistical error bars are not adjusted to reflect the improvements we obtain by using

Eq. (16) so they are likely to be somewhat pessimistic. Errors in the extrapolation to the

K = limit can also be non-negligible. In Tables IV and V we list extrapolations using

two different ranges of K values. The agreement between these two sets of results is

quite good especially given that the largest K value differs by a factor of 1.5 to 2 for each

temperature studied, and the disagreement is comparable to the statistical errors in the

perturbative corrections. Since doubling the values of the largest values of K roughly

halves the contribution to the partition function that must be recovered via extrapolation,

we expect that the observed differences between the results obtained by the two different

extrapolations is comparable to the actual extrapolation error. Quadrature errors in the

numerical evaluation of the action integral and errors from restricting the sampling to lie

within a finite region of space are also present but are expected to be much smaller than

the other errors as we have used very conservative numerical parameters.

The agreement we obtain between the FPIMC partition functions and the results

of Partridge and Schwenke

20

is excellent, with the largest deviation being less than 1%

and seven of the ten deviations being less than 0.2%. At the two highest temperatures the

small deviations we observe are still much larger than the expected errors in the FPIMC

calculations. The calculations of Partridge and Schwenke

20

are likely slightly too low at

the highest temperatures since their partition function calculations were limited to

13

170,625 eigenvalues. At the other eight temperatures the observed deviations are all

comparable to the FPIMC statistical error estimates. (Note that this is strictly a test of the

two methods of calculating the partition function for a given potential; we make no

attempt here to sort out the accuracy of various potentials.)

For the calculations presented here, the computational cost is dominated by the

low-K calculations, i.e., the cost of calculating Q

[K]

(T). At high temperatures (T > 1500

K), extremely accurate results can be obtained at modest cost. At lower temperatures the

calculations become substantially more expensive, and we chose not to converge the

results as tightly. The statistical error at 296 K is a factor of 20 higher than the statistical

error at 4000 K even though we used 200 times as many samples at the lower

temperature. To achieve the same level of accuracy for the results at 296 K would

require about 80,000 times as many samples as were used at 4000 K. The quadrature

requirements also increase at low temperature in proportion with the increasingly large

values of K required to get qualitatively accurate results. Thus the calculations at 296 K

would require about 1 million times as many potential function evaluations to achieve the

same relative error in Q(T) as was achieved at 4000 K.

The extrapolated corrections, Q

corr,K

(T), calculated here range from 2 to 34% of

the magnitude of the accurate partition function. Given these large magnitudes, the high

accuracy we observe is remarkable. In order to achieve the same degree of convergence

without using the extrapolation and perturbative correction schemes presented here we

would require K values that are at least 20 to 100 times as large as the K values presently

used. (This is a very conservative estimate because we are comparing only the truncation

error of a large-K calculation to the total error [extrapolation, statistical, etc.] of the final

14

results of our full calculations.) Since higher K involves sampling more degrees of

freedom and since the quadrature requirements scale linearly with K, the final cost for a

straightforward calculation would increase by at least the same factors. Thus the methods

presented here provide a considerable reduction in the computational cost.

Table VII presents the final internal free energies in order to illustrate the size of

the uncertainty on the energy scale, which is the familiar scale for applications. Clearly

the statistical errors are now smaller than experimental error, and the accuracy of the

calculation is limited almost entirely by the accuracy of the potential energy functions.

The results presented here are especially encouraging because the effort in the

diagonalization method used in Ref. 19 grows as a high power of system size whereas

effort for the path integral approach increases slowly with system size. For triatomic

systems at very low temperatures the diagonalization method requires only a few low

eigenvalues and is clearly the method of choice, but for high temperatures the present

method is considerably less expensive.

IV. CONCLUDING REMARKS

Perturbation theory and extrapolation methods are widely used in many areas of

physics. With respect to Monte Carlo algorithms though, although perturbation methods

are widely used,

22

extrapolation methods are less common, probably because they

involve taking small differences between large numbers, and these differences are easily

overwhelmed by statistical errors. We have shown, however, that extrapolation can be

carried out very stably by using the same random number stream to calculate all the

results that are to be extrapolated. The present application involves a novel type of

15

perturbation and extrapolation in which the high-frequency components of the path

integrals are a perturbation on the results obtained by neglecting these high-frequency

components. Similar approaches might be useful for other forms

22-24

of thermodynamic

perturbation theory.

By using both perturbation and extrapolation techniques we have presented two

easily implemented schemes to address the high computational costs associated with the

slow convergence of Fourier path-integral Monte Carlo methods with respect to the size

of the Fourier space. These methods were used to calculate very accurate partition

functions and free energies for water over a temperature range of 2964000 K. Savings

compared to FPIMC calculations without these new techniques are about a factor of 20 to

100. These new techniques hold considerable promise for calculating accurate partition

functions of much larger systems than previously studied.

ACKNOWLEDGMENTS

The authors are grateful to David Schwenke, Jonathan Tennyson, and Robert

Topper for comments on the original manuscript. A portion of this work was supported

by the Division of Chemical Sciences, Office of Basis Energy Sciences, of the U.S.

Department of Energy and performed in the William R. Wiley Environmental Molecular

Sciences Laboratory, a national scientific user facility sponsored by the Department of

Energy's Office of Biological and Environmental Research and located at Pacific

Northwest National Laboratory. Pacific Northwest National Laboratory is operated for

the Department of Energy by Battelle. Additional support was provided by the National

Science Foundation under grant number CHE97-25965.

16

References

1

R. P. Feynman and A. R. Hibbs, Quantum mechanics and path integrals (McGraw-Hill,

New York, 1965).

2

R. P. Feynman, Statistical Mechanics (Benjamin, New York, 1972).

3

W. H. Miller, J. Chem. Phys. 63, 1166 (1975).

4

J. D. Doll and D. L. Freeman, J. Chem. Phys. 80, 2239 (1980).

5

R. D. Coalson, J. Chem. Phys. 85, 926 (1986).

6

J. D. Doll, R. D. Coalson, and D. L. Freeman, Phys. Rev. Lett. 55, 1 (1986).

7

R. D. Coalson, D. L. Freeman, and J. D. Doll, J. Chem. Phys. 85, 4576 (1986).

8

D. L. Freeman and J. D. Doll, Adv. Chem. Phys. 70B, 139 (1988).

9

J. D. Doll, D. L. Freeman, and T. Beck, Adv. Chem. Phys. 78, 61 (1990).

10

R. Q. Topper and D. G. Truhlar, J. Chem. Phys. 97, 3647 (1992).

11

R. Q. Topper, G. J. Tawa, and D. G. Truhlar, J. Chem. Phys. 97, 3668 (1992).

12

R. Q. Topper, Q. Zhang, Y.-P. Liu, and D. G. Truhlar, J. Chem. Phys. 98, 4991 (1993).

13

R. Q. Topper, Adv. Chem. Phys. 105, 117 (1999).

14

J. Srinivasan, Y. L. Volobuev, S. L. Mielke, and D. G. Truhlar, Comp. Phys. Comm.,

in press.

15

M. Eleftheriou, J. D. Doll, E. Curotto, and D. L. Freeman, J. Chem. Phys. 110, 6657

(1999).

16

T. L. Hill, An Introduction to Statistical Thermodynamics (Addison-Wesley, Reading,

MA, 1960) p.119.

17

W. Forst, Theory of Unimolecular Reactions (Academic Press, New York, 1973).

17

18

D. A. McQuarrie, Statistical Mechanics (Harper & Row, New York, 1973) chapters 5

and 9.

19

L. Halonen, Adv. Chem. Phys. 104, 41 (1998).

20

H. Partridge and D. W. Schwenke, J. Chem. Phys. 106, 4618 (1997).

21

G. J. Harris, S. Viti, H. Y. Mussa, and J. Tennyson, J. Chem. Phys. 109, 7197 (1998).

22

T. P. Straatsma and J. A. McCammon, Annu. Rev. Phys. Chem. 43, 407 (1992).

23

W. Witschel and J. Bohmann, J. Phys. A 13, 275 (1980).

24

W. Witschel, Phys. Lett. 77A, 107 (1980).

18

Table I. The parameters used for calculating Q

[K]

(T).

________________________________________________________________________

parameter note 296 K 500 K 750 K 1000 K 15004000 K

________________________________________________________________________

K a 128 64 32 32 8

N

samples b

110

10

410

8

210

8

110

8

510

7

N

initial

c 110

9

210

7

110

7

510

6

510

5

N

PU

d 500 100 100 100 100

l

e 80 80 80 80 80

u

f 140 140 140 140 160

N

QR

g 6 2 1 1 1

N

QL

g 64 64 64 64 32

N

strata

h 20 20 20 20 20

N

sweeps

i 20 20 20 20 20

OH

j 0.17 0.17 0.17 0.17 0.17

HH

k 0.35 0.35 0.35 0.35 0.35

S

Vmax

l 7 20 20 none none

S

Vave

m 0.7 1.2 1.2 none none

S

EVave

n 1.5 2 2 none none

S

Nmin

n 8 8 8 none none

________________________________________________________________________

a)

the number of Fourier coefficients used to expand the paths

b)

the total number of Monte Carlo samples

c)

the number of Monte Carlo samples used before stratified sampling

d

)the number of times the relative paths are reused

19

e)

the lower limit of the hyperannulus (in mass-scaled bohrs) that defines the allowed

configuration space. The scaling mass in the mass-scaled coordinates was set at = 1 m

e

where m

e

is the mass of an electron.

f)

the upper limit of the hyperannulus (in mass-scaled bohrs) that defines the allowed

configuration space

g)

The action integral is evaluated using N

QR

repetitions of N

QL

-point Gauss-Legendre

quadrature.

h)

the number of strata used in the stratified sampling

i)

the number of the times the optimal sampling estimates are recalculated in the

adaptively optimized stratified sampling scheme

j)

the OH gaussian width parameter (in bohrs, not mass scaled) in the importance function

k)

the HH gaussian width parameter (in bohrs, not mass scaled) in the importance function

l)

If the potential energy (in eV) is above this value for any quadrature point the evaluation

of the action integral is aborted.

m)

The evaluation of the action integral is aborted once the mean potential energy (in eV)

of the path is known to exceed this value.

n

)

The evaluation of the action integral is aborted when both the estimated mean potential

energy (in eV) of the path exceeds S

EVave

eV, and a minimum of S

Nmin

quadrature

points have been evaluated.

20

Table II. Parameters used in the perturbative corrections.

a

________________________________________________________________________

parameter 296 K 500 K 750 K 1000 K 15004000 K

________________________________________________________________________

K 128 64 32 32 8

K 128384 64256 32128 32128 864

N

samples

210

8

110

7

310

6

110

6

510

5

N

initial

210

7

110

6

310

5

110

5

510

4

N

QR

9 8 4 4 1

N

QL

64 64 64 64 128

________________________________________________________________________

a

Unlisted parameters are the same as in Table I.

21

Table III. Partition functions and 2 statistical errors for the two calculations with

Fourier expansion length of K.

___________________________________________________________________________________________________

T K Q T

K,

( )

S

Q T

K,

( )

L

___________________________________________________________________________________________________

296 128 (9.42 0.19)10

9

(9.540 0.029)10

9

500 64 (1.881 0.018)10

4

(1.8972 0.0030)10

4

750 32 (3.036 0.019)10

2

(3.0252 0.0025)10

2

1000 32 0.4306 0.0029 0.42628 0.00030

1500 8 9.340 0.053 9.3755 0.0059

2000 8 51.64 0.21 51.513 0.026

2500 8 173.70 0.56 173.880 0.075

3000 8 449.4 1.3 449.22 0.18

3500 8 979.0 2.5 982.24 0.37

4000 8 1914.4 5.8 1915.83 0.75

___________________________________________________________________________________________________

22

Table IV. High-k corrections, Q T

K K corr, ,

( )

, with 2 statistical errors for specific K and extrapolated to the K = limit for

T = 2961000 K.

____________________________________________________________________________________________________________

K T = 296 K T = 500 K T = 750 K T = 1000 K

___________________________________________________________________________________________________________

64 (2.603 0.017)10

3

(2.111 0.015)10

2

96 (3.427 0.022)10

3

(2.794 0.019)10

2

128 (1.829 0.018)10

5

(3.834 0.025)10

3

(3.135 0.022)10

2

192 (2.402 0.024)10

5

256 (1.289 0.026)10

9

(2.682 0.027)10

5

384 (1.680 0.034)10

9

a

(2.401 0.049)10

9

b

(3.495 0.035)10

5

(5.035 0.033)10

3

(4.161 0.029)10

2

c

(3.494 0.035)10

5

b

(5.012 0.033)10

3

(4.128 0.028)10

2

___________________________________________________________________________________________________________

a

extrapolated using the three highest values of K in the table (this is the final calculation)

b

the extrapolation at 296 K and the second extrapolation at 500 K include the point with K = K and Q T

K K corr, ,

( )

= 0.

c

extrapolated using the second, third, and fourth highest values of K in the table (this is a test for comparison to the results of the

previous line)

23

Table V. High-k corrections, Q T

K K corr, ,

( )

, with 2 statistical errors for specific K and extrapolated to the K = limit for

T = 15004000 K.

___________________________________________________________________________________________________________

K T = 1500 K T = 2000 K T = 2500 K T = 3000 K T = 3500 K T = 4000 K

___________________________________________________________________________________________________________

12 0.4889 0.0038 1.518 0.009 3.220 0.018 5.712 0.031 9.026 0.051 13.29 0.09

16 0.7325 0.0050 2.288 0.012 4.875 0.023 8.681 0.038 13.704 0.062 20.21 0.11

20 0.8778 0.0058 2.753 0.014 5.882 0.025 10.469 0.042 16.537 0.067 24.40 0.12

32 1.0961 0.0069 3.452 0.016 7.396 0.029 13.216 0.048 20.862 0.075 30.77 0.13

64 1.2759 0.0078 4.039 0.018 8.676 0.033 15.512 0.053 24.513 0.082 36.16 0.14

a

1.4538 0.0089 4.631 0.021 9.973 0.038 17.814 0.061 28.207 0.094 41.63 0.17

b

1.4607 0.0090 4.620 0.021 9.926 0.038 17.962 0.061 28.268 0.094 41.60 0.17

___________________________________________________________________________________________________________

a

extrapolated using the three highest values of K in the table (this is the final calculation)

b

extrapolated using the second, third, and fourth highest values of K in the table (this is a test for comparison to the results of the

previous line)

24

Table VI. Comparison of FPIMC partition functions to those of Partridge and Schwenke.

____________________________________________________________________________________________________________

T Q(T) 2 % error % difference

_________________________ __________ _______________

(K) FPIMC PS

a

FPIMC FPIMC vs. PS

a

_______________________________________________________________________________________

296 (7.107 0.057)10

9

7.05310

9

0.80 0.77

500 (1.5446 0.0046)10

4

1.542810

4

0.30 0.12

750 (2.5235 0.0041)10

2

2.524810

2

0.16 0.05

1000 0.38509 0.00041 0.38493 0.11 0.04

1500 7.9161 0.0098 7.9285 0.12 0.16

2000 46.893 0.033 46.893 0.071 0.00

2500 163.896 0.084 163.789 0.051 0.07

3000 431.41 0.19 431.10 0.043 0.07

3500 953.94 0.38 951.05 0.040 0.30

4000 1874.18 0.77 1855.88 0.041 0.99

_______________________________________________________________________________________

a

Ref. 20

25

Table VII. Absolute internal free energies (kcal/mol).

__________________________________________________

T(K) present Ref. 20

__________________________________________________

296 11.036 0.005 11.041

500 8.719 0.003 8.721

750 5.484 0.002 5.483

1000 1.896 0.002 1.896

1500 6.167 0.004 6.172

2000 15.293 0.003 15.293

2500 25.333 0.003 25.330

3000 36.169 0.003 36.165

3500 47.717 0.003 47.696

4000 59.901 0.003 59.823

__________________________________________________

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