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lammps/doc/src/fix_bond_react.txt
Axel Kohlmeyer d359beb170 Merge pull request #1215 from jrgissing/bond/react-doc-corrections,mostly-formatting
Bond/react doc corrections,mostly formatting
2018-11-20 10:50:55 -05:00

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"LAMMPS WWW Site"_lws - "LAMMPS Documentation"_ld - "LAMMPS Commands"_lc :c
:link(lws,http://lammps.sandia.gov)
:link(ld,Manual.html)
:link(lc,Commands_all.html)
:line
fix bond/react command :h3
[Syntax:]
fix ID group-ID bond/react common_keyword values ...
react react-ID react-group-ID Nevery Rmin Rmax template-ID(pre-reacted) template-ID(post-reacted) map_file individual_keyword values ...
react react-ID react-group-ID Nevery Rmin Rmax template-ID(pre-reacted) template-ID(post-reacted) map_file individual_keyword values ...
react react-ID react-group-ID Nevery Rmin Rmax template-ID(pre-reacted) template-ID(post-reacted) map_file individual_keyword values ...
... :pre
ID, group-ID are documented in "fix"_fix.html command. Group-ID is ignored. :ulb,l
bond/react = style name of this fix command :l
zero or more common keyword/value pairs may be appended directly after 'bond/react' :l
these apply to all reaction specifications (below) :l
common_keyword = {stabilization} :l
{stabilization} values = {no} or {yes} {group-ID} {xmax}
{no} = no reaction site stabilization
{yes} = perform reaction site stabilization
{group-ID} = user-assigned prefix for the dynamic group of non-reacting atoms
{xmax} = xmax value that is used by an internally-created "nve/limit"_fix_nve_limit.html integrator :pre
react = mandatory argument indicating new reaction specification :l
react-ID = user-assigned name for the reaction :l
react-group-ID = only atoms in this group are considered for the reaction :l
Nevery = attempt reaction every this many steps :l
Rmin = bonding pair atoms must be separated by more than Rmin to initiate reaction (distance units) :l
Rmax = bonding pair atoms must be separated by less than Rmax to initiate reaction (distance units) :l
template-ID(pre-reacted) = ID of a molecule template containing pre-reaction topology :l
template-ID(post-reacted) = ID of a molecule template containing post-reaction topology :l
map_file = name of file specifying corresponding atom-IDs in the pre- and post-reacted templates :l
zero or more individual keyword/value pairs may be appended to each react argument :l
individual_keyword = {prob} or {stabilize_steps} or {update_edges} :l
{prob} values = fraction seed
fraction = initiate reaction with this probability if otherwise eligible
seed = random number seed (positive integer)
{stabilize_steps} value = timesteps
timesteps = number of timesteps to apply the internally-created "nve/limit"_fix_nve_limit.html fix to reacting atoms
{update_edges} value = {none} or {charges} or {custom}
none = do not update topology near the edges of reaction templates
charges = update atomic charges of all atoms in reaction templates
custom = force the update of user-specified atomic charges :pre
:ule
[Examples:]
molecule mol1 pre_reacted_topology.txt
molecule mol2 post_reacted_topology.txt
fix 5 all bond/react react myrxn1 all 1 0 3.25 mol1 mol2 map_file.txt :pre
molecule mol1 pre_reacted_rxn1.txt
molecule mol2 post_reacted_rxn1.txt
molecule mol3 pre_reacted_rxn2.txt
molecule mol4 post_reacted_rxn2.txt
fix 5 all bond/react stabilization yes nvt_grp .03 &
react myrxn1 all 1 0 3.25 mol1 mol2 map_file_rxn1.txt prob 0.50 12345 &
react myrxn2 all 1 0 2.75 mol3 mol4 map_file_rxn2.txt prob 0.25 12345
fix 6 nvt_grp_REACT nvt temp 300 300 100 # set thermostat after bond/react :pre
[Description:]
Initiate complex covalent bonding (topology) changes. These topology
changes will be referred to as 'reactions' throughout this
documentation. Topology changes are defined in pre- and post-reaction
molecule templates and can include creation and deletion of bonds,
angles, dihedrals, impropers, bond-types, angle-types, dihedral-types,
atom-types, or atomic charges.
Fix bond/react does not use quantum mechanical (eg. fix qmmm) or
pairwise bond-order potential (eg. Tersoff or AIREBO) methods to
determine bonding changes a priori. Rather, it uses a distance-based
probabilistic criteria to effect predetermined topology changes in
simulations using standard force fields.
This fix was created to facilitate the dynamic creation of polymeric,
amorphous or highly cross-linked systems. A suggested workflow for
using this fix is: 1) identify a reaction to be simulated 2) build a
molecule template of the reaction site before the reaction has
occurred 3) build a molecule template of the reaction site after the
reaction has occurred 4) create a map that relates the
template-atom-IDs of each atom between pre- and post-reaction molecule
templates 5) fill a simulation box with molecules and run a simulation
with fix bond/react.
Only one 'fix bond/react' command can be used at a time. Multiple
reactions can be simultaneously applied by specifying multiple {react}
arguments to a single 'fix bond/react' command. This syntax is
necessary because the 'common keywords' are applied to all reactions.
The {stabilization} keyword enables reaction site stabilization.
Reaction site stabilization is performed by including reacting atoms
in an internally-created fix "nve/limit"_fix_nve_limit.html time
integrator for a set number of timesteps given by the
{stabilize_steps} keyword. While reacting atoms are being time
integrated by the internal nve/limit, they are prevented from being
involved in any new reactions. The {xmax} value keyword should
typically be set to the maximum distance that non-reacting atoms move
during the simulation.
The group-ID set using the {stabilization} keyword can be an existing
static group or a previously-unused group-ID. It cannot be specified
as 'all'. If the group-ID is previously unused, the fix bond/react
command creates a "dynamic group"_group.html that is initialized to
include all atoms. If the group-ID is that of an existing static
group, the group is used as the parent group of new,
internally-created dynamic group. In both cases, this new dynamic
group is named by appending '_REACT' to the group-ID, e.g.
nvt_grp_REACT. By specifying an existing group, you may thermostat
constant-topology parts of your system separately. The dynamic group
contains only non-reacting atoms at a given timestep, and therefore
should be used by a subsequent system-wide time integrator such as
nvt, npt, or nve, as shown in the second example above. The time
integration command should be placed after the fix bond/react command
due to the internal dynamic grouping performed by fix bond/react.
NOTE: If the group-ID is an existing static group, react-group-IDs
should also be specified as this static group, or a subset.
NOTE: If the group-ID is previously unused, the internally-created
group applies to all atoms in the system, i.e. you should generally
not have a separate thermostat which acts on the 'all' group, or any
other group.
The following comments pertain to each {react} argument (in other
words, can be customized for each reaction, or reaction step):
A check for possible new reaction sites is performed every {Nevery}
timesteps.
Two conditions must be met for a reaction to occur. First a bonding
atom pair must be identified. Second, the topology surrounding the
bonding atom pair must match the topology of the pre-reaction
template. If both these conditions are met, the reaction site is
modified to match the post-reaction template.
A bonding atom pair will be identified if several conditions are met.
First, a pair of atoms I,J within the specified react-group-ID of type
itype and jtype must separated by a distance between {Rmin} and
{Rmax}. It is possible that multiple bonding atom pairs are
identified: if the bonding atoms in the pre-reacted template are not
1-2, 1-3, or 1-4 neighbors, the closest bonding atom partner is set as
its bonding partner; otherwise, the farthest potential partner is
chosen. Then, if both an atom I and atom J have each other as their
nearest bonding partners, these two atoms are identified as the
bonding atom pair of the reaction site. Once this unique bonding atom
pair is identified for each reaction, there could two or more
reactions that involve a given atom on the same timestep. If this is
the case, only one such reaction is permitted to occur. This reaction
is chosen randomly from all potential reactions. This capability
allows e.g. for different reaction pathways to proceed from identical
reaction sites with user-specified probabilities.
The pre-reacted molecule template is specified by a molecule command.
This molecule template file contains a sample reaction site and its
surrounding topology. As described below, the bonding atom pairs of
the pre-reacted template are specified by atom ID in the map file. The
pre-reacted molecule template should contain as few atoms as possible
while still completely describing the topology of all atoms affected
by the reaction. For example, if the force field contains dihedrals,
the pre-reacted template should contain any atom within three bonds of
reacting atoms.
Some atoms in the pre-reacted template that are not reacting may have
missing topology with respect to the simulation. For example, the
pre-reacted template may contain an atom that would connect to the
rest of a long polymer chain. These are referred to as edge atoms, and
are also specified in the map file. When the pre-reaction template
contains edge atoms, not all atoms, bonds, charges, etc. specified in
the reaction templates will be updated. Specifically, topology that
involves only atoms that are 'too near' to template edges will not be
updated. The definition of 'too near the edge' depends on which
interactions are defined in the simulation. If the simulation has
defined dihedrals, atoms within two bonds of edge atoms are considered
'too near the edge.' If the simulation defines angles, but not
dihedrals, atoms within one bond of edge atoms are considered 'too
near the edge.' If just bonds are defined, only edge atoms are
considered 'too near the edge.'
Note that some care must be taken when a building a molecule template
for a given simulation. All atom types in the pre-reacted template
must be the same as those of a potential reaction site in the
simulation. A detailed discussion of matching molecule template atom
types with the simulation is provided on the "molecule"_molecule.html
command page.
The post-reacted molecule template contains a sample of the reaction
site and its surrounding topology after the reaction has occurred. It
must contain the same number of atoms as the pre-reacted template. A
one-to-one correspondence between the atom IDs in the pre- and
post-reacted templates is specified in the map file as described
below. Note that during a reaction, an atom, bond, etc. type may
change to one that was previously not present in the simulation. These
new types must also be defined during the setup of a given simulation.
A discussion of correctly handling this is also provided on the
"molecule"_molecule.html command page.
The map file is a text document with the following format:
A map file has a header and a body. The header of map file the
contains one mandatory keyword and two optional keywords. The
mandatory keyword is 'equivalences' and the optional keywords are
'edgeIDs' and 'customIDs':
N {equivalences} = # of atoms N in the reaction molecule templates
N {edgeIDs} = # of edge atoms N in the pre-reacted molecule template
N {customIDs} = # of atoms N that are specified for a custom update :pre
The body of the map file contains two mandatory sections and two
optional sections. The first mandatory section begins with the keyword
'BondingIDs' and lists the atom IDs of the bonding atom pair in the
pre-reacted molecule template. The second mandatory section begins
with the keyword 'Equivalences' and lists a one-to-one correspondence
between atom IDs of the pre- and post-reacted templates. The first
column is an atom ID of the pre-reacted molecule template, and the
second column is the corresponding atom ID of the post-reacted
molecule template. The first optional section begins with the keyword
'EdgeIDs' and lists the atom IDs of edge atoms in the pre-reacted
molecule template. The second optional section begins with the keyword
'Custom Edges' and allows for forcing the update of a specific atom's
atomic charge. The first column is the ID of an atom near the edge of
the pre-reacted molecule template, and the value of the second column
is either 'none' or 'charges.' Further details are provided in the
discussion of the 'update_edges' keyword.
A sample map file is given below:
:line
# this is a map file :pre
2 edgeIDs
7 equivalences :pre
BondingIDs :pre
3
5 :pre
EdgeIDs :pre
1
7 :pre
Equivalences :pre
1 1
2 2
3 3
4 4
5 5
6 6
7 7 :pre
:line
Once a reaction site has been successfully identified, data structures
within LAMMPS that store bond topology are updated to reflect the
post-reacted molecule template. All force fields with fixed bonds,
angles, dihedrals or impropers are supported.
A few capabilities to note: 1) You may specify as many {react}
arguments as desired. For example, you could break down a complicated
reaction mechanism into several reaction steps, each defined by its
own {react} argument. 2) While typically a bond is formed or removed
between the bonding atom pairs specified in the pre-reacted molecule
template, this is not required. 3) By reversing the order of the pre-
and post- reacted molecule templates in another {react} argument, you
can allow for the possibility of one or more reverse reactions.
The optional keywords deal with the probability of a given reaction
occurring as well as the stable equilibration of each reaction site as
it occurs.
The {prob} keyword can affect whether an eligible reaction actually
occurs. The fraction setting must be a value between 0.0 and 1.0. A
uniform random number between 0.0 and 1.0 is generated and the
eligible reaction only occurs if the random number is less than the
fraction.
The {stabilize_steps} keyword allows for the specification of how many
timesteps a reaction site is stabilized before being returned to the
overall system thermostat.
In order to produce the most physical behavior, this 'reaction site
equilibration time' should be tuned to be as small as possible while
retaining stability for a given system or reaction step. After a
limited number of case studies, this number has been set to a default
of 60 timesteps. Ideally, it should be individually tuned for each fix
reaction step. Note that in some situations, decreasing rather than
increasing this parameter will result in an increase in stability.
The {update_edges} keyword can increase the number of atoms whose
atomic charges are updated, when the pre-reaction template contains
edge atoms. When the value is set to 'charges,' all atoms' atomic
charges are updated to those specified by the post-reaction template,
including atoms near the edge of reaction templates. When the value is
set to 'custom,' an additional section must be included in the map
file that specifies whether to update charges, on a per-atom basis.
The format of this section is detailed above. Listing a pre-reaction
atom ID with a value of 'charges' will force the update of the atom's
charge, even if it is near a template edge. Atoms not near a template
edge are unaffected by this setting.
A few other considerations:
It may be beneficial to ensure reacting atoms are at a certain
temperature before being released to the overall thermostat. For this,
you can use the internally-created dynamic group named
"bond_react_MASTER_group." For example, adding the following command
would thermostat the group of all atoms currently involved in a
reaction:
fix 1 bond_react_MASTER_group temp/rescale 1 300 300 10 1 :pre
NOTE: This command must be added after the fix bond/react command, and
will apply to all reactions.
Computationally, each timestep this fix operates, it loops over
neighbor lists (for bond-forming reactions) and computes distances
between pairs of atoms in the list. It also communicates between
neighboring processors to coordinate which bonds are created and/or
removed. All of these operations increase the cost of a timestep. Thus
you should be cautious about invoking this fix too frequently.
You can dump out snapshots of the current bond topology via the dump
local command.
:line
[Restart, fix_modify, output, run start/stop, minimize info:]
No information about this fix is written to "binary restart
files"_restart.html, aside from internally-created per-atom
properties. None of the "fix_modify"_fix_modify.html options are
relevant to this fix.
This fix computes one statistic for each {react} argument that it
stores in a global vector, of length 'number of react arguments', that
can be accessed by various "output commands"_Howto_output.html. The
vector values calculated by this fix are "intensive".
These is 1 quantity for each react argument:
(1) cumulative # of reactions occurred :ul
No parameter of this fix can be used with the {start/stop} keywords of
the "run"_run.html command. This fix is not invoked during "energy
minimization"_minimize.html.
[Restrictions:]
This fix is part of the USER-MISC package. It is only enabled if
LAMMPS was built with that package. See the "Build
package"_Build_package.html doc page for more info.
[Related commands:]
"fix bond/create"_fix_bond_create.html, "fix
bond/break"_fix_bond_break.html, "fix bond/swap"_fix_bond_swap.html,
"dump local"_dump.html, "special_bonds"_special_bonds.html
[Default:]
The option defaults are stabilization = no, prob = 1.0, stabilize_steps = 60, update_edges = none
:line
:link(Gissinger)
[(Gissinger)] Gissinger, Jensen and Wise, Polymer, 128, 211 (2017).