is use of a restraint for pmf calculations valid?

garold g.murd... at gmail.com
Wed Mar 14 16:18:28 UTC 2012


Dear all,

I am calculating a PMF curve of a molecule solvated in water, as a
function of depth within the water slab.  I am new to this type of
calculation so please forgive me if my questions seem trivial.  For a
first attempt, I am wondering if the direct approach of using a
harmonic restraint on the center-of-mass of the solute molecule with
respect to a fixed point in the slab (z_s) is valid.  Thus, my
restraining potential (on COLVAR 2) is just K*(z-z_s)**2 and force of
the restraint is 2*K*(z-z_s).  I have set K to 1 au (hartree/bohr**2,
I have also tried 0.1 and 0.01).  I can easily post-process what the
force is at any frame from the z value printed out (COM of solute
molecule).  Then I average the force over the run (after a suitable
equilibration period).  The use of an explicit restraint seems simpler
than not using one and instead printing out the lagrange multiplier
coming from the Shake algorithm.  The PMF can be obtained as usual
from integrating the average force on the solute (negative of the
restraint force).  I have some preliminary results with such
calculations and would like to know if the approach is reasonable
before going further.  Please also advise me if my input file (see
below) seems reasonable.  For now I using classical, polarizable
potentials.

Thank you,
Garold

---------------------------------------------------------------------------------------------------------------------------------------------------------------------
@SET BASE_NAME run
@SET ID 01
&FORCE_EVAL
  METHOD FIST
  &MM
    &POISSON
      &EWALD
        EWALD_TYPE EWALD
        ALPHA 0.3
        GMAX 31 31 143 ! 25
        O_SPLINE 6
        &MULTIPOLES T
          MAX_MULTIPOLE_EXPANSION DIPOLE
          POL_SCF SELF_CONSISTENT
          EPS_POL 1.0e-6
          MAX_IPOL_ITER 100
        &END MULTIPOLES
      &END EWALD
    &END POISSON
    &FORCEFIELD
      &SPLINE
        EMAX_SPLINE 10000000000.0
        RCUT_NB 12.00
      &END SPLINE
      &BEND
        ATOMS      H     O     H
       THETA0     [deg] 109.500
        !K          [rad^2kjmol] 627.600
        K          [rad^2kjmol] 0.000
        KIND   G87
      &END BEND
      &BEND
        ATOMS      H     O     M
        THETA0     [deg]  54.750
        !K          [rad^2kjmol]  418.400
        K          [rad^2kjmol]  0.000
        KIND   G87
      &END BEND
      &BEND
        ATOMS      M     H     O
        THETA0     [deg] 109.500
        K          [rad^2kjmol] 0.000
        KIND   G87
      &END BEND
      &BEND
        ATOMS      M     H     H
        THETA0     [deg] 109.500
        K          [rad^2kjmol] 0.000
        KIND   G87
      &END BEND
      &BEND
        ATOMS      O     H     H
        THETA0     [deg] 109.500
        K          [rad^2kjmol] 0.000
        KIND   G87
      &END BEND
      &BEND
        ATOMS      O     M     H
        THETA0     [deg] 109.500
        K          [rad^2kjmol] 0.000
        KIND   G87
      &END BEND
      &BEND
        ATOMS      H     M     H
        THETA0     [deg] 109.500
        K          [rad^2kjmol] 0.000
        KIND   G87
      &END BEND
      &BEND
        ATOMS O2 N2 O2
        K 0.
        THETA0 1.8
      &END BEND
      &BOND
        ATOMS O H
        K      [nm^-2kjmol] 502080.0
        !K      [nm^-2kjmol] 0.0
        R0     [nm] 0.09572
        KIND   G87
      &END BOND
      &BOND
        ATOMS O M
        !K      [nm^-2kjmol]  753120.0
        K      [nm^-2kjmol]  00.0
        R0     [nm]  0.01750
        KIND   G87
      &END BOND
      &BOND
        ATOMS H H
        K      [nm^-2kjmol]  000000.0
        R0     [nm]  0.01750
        KIND   G87
      &END BOND
      &BOND
        ATOMS H M
        K      [nm^-2kjmol]  000000.0
        R0     [nm]  0.01750
        KIND   G87
      &END BOND
      &BOND
        ATOMS N2 O2
        K 0.
        R0 1.8
      &END BOND
      &CHARGE
        ATOM O
        CHARGE 0.000000
      &END CHARGE
      &CHARGE
        ATOM H
        CHARGE 0.5190
      &END CHARGE
      &CHARGE
        ATOM M
        CHARGE -1.038
      &END CHARGE
      &DIPOLE
        ATOM M
        APOL 1.444
      &END DIPOLE
      &CHARGE
        ATOM N2
        CHARGE 0.28
      &END CHARGE
      &CHARGE
        ATOM O2
        CHARGE -0.14
      &END CHARGE
      &NONBONDED
        &LENNARD-JONES
          ATOMS      O O
          EPSILON    [kcalmol] 0.1825
          SIGMA      [nm] 3.234E-01
        &END LENNARD-JONES
        &LENNARD-JONES
          ATOMS      O M
          EPSILON    0.0
          SIGMA      0.1
        &END LENNARD-JONES
        &LENNARD-JONES
          ATOMS      O H
          EPSILON    0.0
          SIGMA      0.1
        &END LENNARD-JONES
        &LENNARD-JONES
          ATOMS      H H
          EPSILON    0.0
          SIGMA      0.1
        &END LENNARD-JONES
        &LENNARD-JONES
          ATOMS      H M
          EPSILON    0.0
          SIGMA      0.1
        &END LENNARD-JONES
        &LENNARD-JONES
          ATOMS      M M
          EPSILON    0.0
          SIGMA      0.1
        &END LENNARD-JONES
        &LENNARD-JONES
          ATOMS N2 N2
          EPSILON 78.198
          SIGMA 3.166
        &END LENNARD-JONES
        &LENNARD-JONES
          ATOMS N2 O2
          EPSILON 0.0
          SIGMA 3.6705
        &END LENNARD-JONES
        &LENNARD-JONES
          ATOMS O2 O2
          EPSILON 0.0
          SIGMA 3.30523
        &END LENNARD-JONES
        &WILLIAMS
          ATOMS O N2
          A [kcalmol] 56844.355799
          B [angstrom^-1] 3.674000
          C [angstrom^6kcalmol] 303.547232
        &END WILLIAMS
        &WILLIAMS
          ATOMS O O2
          A [kcalmol] 60718.546747
          B [angstrom^-1] 3.798000
          C [angstrom^6kcalmol] 243.535105
        &END WILLIAMS
        &WILLIAMS
          ATOMS H N2
          A [kcalmol] 9600.936470
          B [angstrom^-1] 3.420000
          C [angstrom^6kcalmol] 96.538689
        &END WILLIAMS
        &WILLIAMS
          ATOMS H O2
          A [kcalmol] 10255.282195
          B [angstrom^-1] 3.544000
          C [angstrom^6kcalmol] 77.452723
        &END WILLIAMS
        &WILLIAMS
          ATOMS M N2
          A [kcalmol] 0.0
          B [angstrom^-1] 0.0
          C [angstrom^6kcalmol] 0.0
        &END WILLIAMS
        &WILLIAMS
          ATOMS M O2
          A [kcalmol] 0.0
          B [angstrom^-1] 0.0
          C [angstrom^6kcalmol] 0.0
        &END WILLIAMS
      &END NONBONDED
    &END FORCEFIELD
  &END MM
  &SUBSYS
    &CELL
      ABC 15.0 15.0 71.44
    &END CELL
    &COORD
O    3.1662481629706754E+01    3.8212607304406419E+01
4.6145495800727794E+01 H2O 1
H    3.2370761924609546E+01    3.7649888127503075E+01
4.6458414083339115E+01 H2O 1
H    3.0947883930321868E+01    3.8065366918359565E+01
4.6765094135574984E+01 H2O 1
M    3.1661322487315456E+01    3.8082341112356445E+01
4.6316597642464885E+01 H2O 1
O   -2.2427516707894708E+00    1.8141648260858169E+01
3.2873224002628270E+01 H2O 2
H   -2.4001057532262369E+00    1.7199422463306000E+01
3.2812545019755355E+01 H2O 2
H   -3.1165745469166026E+00    1.8532055176187448E+01
3.2857484834454446E+01 H2O 2
M   -2.4319561026075309E+00    1.8040398347145139E+01
3.2859202497658337E+01 H2O 2
O    1.7436691005838029E-01    3.1843195435862381E+01
4.8711658036883598E+01 H2O 3
H    7.2474912269787284E-01    3.1157291690181463E+01
4.8333706755015449E+01 H2O 3
H   -5.8818366249847054E-01    3.1883779640067164E+01
4.8134508795822704E+01 H2O 3
M    1.3543741919403809E-01    3.1724789650926954E+01
4.8536412410738507E+01 H2O 3
.
.
.
[200 molecule coordinates removed]
.
.
.
.
O    2.1548881835647431E+00    2.4479166362552618E+01
2.0991429221689963E+01 H2O 213
H    2.5225875195388769E+00    2.4517118796527051E+01
2.1874372317746786E+01 H2O 213
H    2.6206746315755836E+00    2.3757683165022637E+01
2.0568656611027709E+01 H2O 213
M    2.3078194558140108E+00    2.4353749431273627E+01
2.1075863124625279E+01 H2O 213
O   -7.0956688752052228E+00    4.2163194469506976E+01
4.7423581212118272E+01 H2O 214
H   -7.9426919155240148E+00    4.2534965312023658E+01
4.7669691166444274E+01 H2O 214
H   -6.4551414437399695E+00    4.2810951598408472E+01
4.7717463860964060E+01 H2O 214
M   -7.1335575072402806E+00    4.2350261499033550E+01
4.7522661193318939E+01 H2O 214
O    5.5548794114490008E+00    2.6354706038205300E+01
5.0074069011426154E+01 H2O 215
H    5.4713169329547178E+00    2.6619254563897609E+01
4.9157955978260077E+01 H2O 215
H    4.6660240621338263E+00    2.6115214639965210E+01
5.0336388926715927E+01 H2O 215
M    5.3764563376279240E+00    2.6359303619176455E+01
4.9954108461137466E+01 H2O 215
N2           7.64284600146           7.50000000000
30.70968697232 NO2
O2           7.43753762385           6.40143134468
31.12711286950 NO2
O2           7.43740493577           8.59856865532
31.12704758148 NO2
    &END COORD
    &COLVAR
      &DISTANCE
        POINTS 1 2
        AXIS Z
        &POINT
          TYPE FIX_POINT
           XYZ 15.1065589017861 14.2580626814867 67.7442647138845
        &END POINT
        &POINT
          TYPE  GEO_CENTER
          ATOMS   1   5   9  13  17  21  25  29  33  37
          ATOMS  41  45  49  53  57  61  65  69  73  77
          ATOMS  81  85  89  93  97 101 105 109 113 117
          ATOMS 121 125 129 133 137 141 145 149 153 157
          ATOMS 161 165 169 173 177 181 185 189 193 197
          ATOMS 201 205 209 213 217 221 225 229 233 237
          ATOMS 241 245 249 253 257 261 265 269 273 277
          ATOMS 281 285 289 293 297 301 305 309 313 317
          ATOMS 321 325 329 333 337 341 345 349 353 357
          ATOMS 361 365 369 373 377 381 385 389 393 397
          ATOMS 401 405 409 413 417 421 425 429 433 437
          ATOMS 441 445 449 453 457 461 465 469 473 477
          ATOMS 481 485 489 493 497 501 505 509 513 517
          ATOMS 521 525 529 533 537 541 545 549 553 557
          ATOMS 561 565 569 573 577 581 585 589 593 597
          ATOMS 601 605 609 613 617 621 625 629 633 637
          ATOMS 641 645 649 653 657 661 665 669 673 677
          ATOMS 681 685 689 693 697 701 705 709 713 717
          ATOMS 721 725 729 733 737 741 745 749 753 757
          ATOMS 761 765 769 773 777 781 785 789 793 797
          ATOMS 801 805 809 813 817 821 825 829 833 837
          ATOMS 841 845 849 853 857
        &END POINT
      &END DISTANCE
    &END COLVAR
    &COLVAR
      &DISTANCE
        POINTS 1 2
        AXIS Z
        &POINT
          TYPE FIX_POINT
          XYZ [angstrom] 0.0 0.0 31.0
        &END POINT
        &POINT
          TYPE  GEO_CENTER
          ATOMS 861 862 863
          WEIGHTS 0.30446162366521585741 0.34776918816739207129
0.34776918816739207129
        &END POINT
      &END DISTANCE
    &END COLVAR
    &PRINT
      &CELL
      &END CELL
    &END PRINT
    &KIND O
      ELEMENT O
      MASS    15.99940
    &END KIND
    &KIND H
      ELEMENT H
      MASS    1.00800
    &END KIND
    &KIND M
      ELEMENT H
      MASS    0.00000
    &END KIND
    &KIND N2
      ELEMENT N
    &END KIND
    &KIND O2
      ELEMENT O
    &END KIND
  &END SUBSYS
  &PRINT
    &GRID_INFORMATION
    &END GRID_INFORMATION
  &END PRINT
&END FORCE_EVAL
&GLOBAL
  PROJECT ${BASE_NAME}-${ID}
  RUN_TYPE MD
! PREFERRED_FFT_LIBRARY  FFTW
  PRINT_LEVEL     MEDIUM
&END GLOBAL
&MOTION
  &MD
    ENSEMBLE NVT
    STEPS 10000
    TIMESTEP 1.0
    TEMPERATURE 300.0
!   TEMP_TOL 50
    &THERMOSTAT
      TYPE NOSE
      REGION MOLECULE
      &NOSE
        LENGTH 3
        YOSHIDA 3
        TIMECON 100
        MTS 2
      &END NOSE
    &END THERMOSTAT
    &PRINT ON
      &ENERGY
        &EACH
          MD 1
        &END EACH
        FILENAME =${BASE_NAME}-${ID}.ener
      &END ENERGY
    &END PRINT
  &END MD
  &PRINT
    &TRAJECTORY ON
      &EACH
        MD 1
      &END EACH
      FILENAME =${BASE_NAME}-${ID}.xyz
      FORMAT XYZ
    &END TRAJECTORY
    &VELOCITIES ON
      &EACH
        MD 1
      &END EACH
      FILENAME =${BASE_NAME}-${ID}_vel.xyz
      FORMAT XYZ
    &END VELOCITIES
    &FORCES ON
      &EACH
        MD 1
      &END EACH
      FILENAME =${BASE_NAME}-${ID}_force.xyz
      FORMAT XYZ
    &END FORCES
    &RESTART ON
      &EACH
        MD 1
      &END EACH
      FILENAME =${BASE_NAME}-${ID}.restart
    &END RESTART
  &END PRINT
  &CONSTRAINT
    &G3X3
      INTERMOLECULAR FALSE
      DISTANCES 1.808845716 1.808845716 2.860459332
      MOLNAME H2O
      ATOMS 1 2 3
    &END G3X3
    &G3X3
      INTERMOLECULAR FALSE
      DISTANCES 2.2544431 2.2544431 4.1519869
      MOLNAME NO2
      ATOMS 1 2 3
    &END G3X3
    &VIRTUAL_SITE
      INTERMOLECULAR FALSE
      ATOMS 4 2 1 3
      PARAMETERS 0.18348396 0.18348396
      MOLNAME H2O
    &END VIRTUAL_SITE
    CONSTRAINT_INIT T
    SHAKE_TOLERANCE 1.0E-12
    ROLL_TOLERANCE 1.0E-10
    #1st - COM alway set to 0.0
    &COLLECTIVE
      COLVAR 1
      INTERMOLECULAR
      TARGET 0.0
      &RESTRAINT
        K 1.0
      &END RESTRAINT
    &END COLLECTIVE
    &COLLECTIVE
      COLVAR 2
      INTERMOLECULAR
      TARGET 0.0
      &RESTRAINT
        K 1.0
      &END RESTRAINT
    &END COLLECTIVE
  &END CONSTRAINT
&END MOTION
&EXT_RESTART
  RESTART_FILE_NAME ./restart
  RESTART_COUNTERS F
  RESTART_AVERAGES F
  RESTART_VEL F
&END EXT_RESTART
---------------------------------------------------------------------------------------------------------------------------------------------------------------------


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