CN107545077A - Judge the method and device of Binary Liquid liquid intersolubility - Google Patents
Judge the method and device of Binary Liquid liquid intersolubility Download PDFInfo
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Abstract
The invention provides a kind of method and device for judging Binary Liquid liquid intersolubility, methods described includes：The molecular structure of two kinds of materials is obtained, and structure optimization is carried out to the molecular structure of described two materials；Described two materials are established at least one member according to preset ratio to wrap；Structure optimization is carried out at least one member bag, chooses the member bag of minimum energy；Molecular dynamics optimization is carried out to the member bag of selection；The molecule, atom or group that two kinds of materials are chosen in member bag after optimization carry out radial distribution function RDF analyses；According to RDF analysis results, the intersolubility of described two materials is judged.The present invention can realize that the method for computer simulation judges Binary Liquid liquid intersolubility, and it is applied widely, simple to operate, equipment requirement is low, result of calculation more accurately and reliably.
Description
Technical field
The present invention relates to computer simulation field, more particularly to a kind of method and device for judging Binary Liquid liquid intersolubility.
Background technology
The intersolubility of two kinds of liquid plays an important role in chemical separating, chemical reaction, solvent modified etc., generally can be with
Judged by consulting handbook acquisition solubility parameter, cohesion energy density, dielectric constant etc..However, considerable chemicals
Matter simultaneously can not obtain its physical parameter by handbook or document, in addition, solubility parameter etc. is a kind of means of qualitative judgement,
For the liquid-liquid system of partial miscibility, property that phasor can quantify, more intuitively representing mixing liquid, so as to instruct to grind
Study carefully and apply.
Generally liquid-liquid phasor can be obtained by the method that laboratory facilities or thermodynamical model calculate.However, experiment
Method drawing diagram needs to consume huge time and manpower, and there may be that chemical substance cost is high, poisonous, purchase is difficult
The problems such as；Liquid-liquid is calculated using thermodynamical model to balance each other, and is chosen suitable model parameter and is established feasible computational methods
It is more difficult process, and needs substantial amounts of experimental data to support.
Can effectively it be solved the above problems using computer Simulation calculation.The simulation being most widely used at present calculates fluid
The method to balance each other is Gibbs systems Monte Carlo (GEMC) method, and the calculating of the method dense fluid is relatively difficult to achieve, uses meter
Calculation machine analogy method calculates liquid-liquid phasor and is rarely reported, therefore, find reliable method calculate intersolubility between two kinds of liquid and
Liquid-liquid phasor is significant.
The content of the invention
The defects of for prior art, the present invention provide a kind of method and device for judging Binary Liquid liquid intersolubility, can
Realize that the method for computer simulation judges Binary Liquid liquid intersolubility, avoid experimentation complex operation, flow in the prior art
Grow, evaporate, moieties are poisonous and calculate the problems such as relatively difficult to achieve.
In a first aspect, the invention provides a kind of method for judging Binary Liquid liquid intersolubility, methods described includes：
S1：The molecular structure of two kinds of materials is obtained, and structure optimization is carried out to the molecular structure of described two materials；
S2：Described two materials are established at least one member according to preset ratio to wrap；
S3：Structure optimization is carried out at least one member bag, chooses the member bag of minimum energy；
S4：Molecular dynamics optimization is carried out to the member bag of selection；
S5：The molecule, atom or group that two kinds of materials are chosen in member bag after optimization carry out radial distribution function RDF
Analysis；
S6：According to RDF analysis results, the intersolubility of described two materials is judged.
Preferably, methods described also includes：
S7：According to the two of the preset ratio kinds of intersolubilities of material at different temperatures, described two things are redefined
The ratio of matter, repeat step S2 to step S6；
S8：According to intersolubility result of described two materials under the conditions of different temperatures and different proportion, generation described two
Binary liquid-liquid phase figure corresponding to kind material.
Preferably, the step S2, including：
According to default mass ratio, the molecular number of described two materials is obtained, according to described under the first preparatory condition
The molecular number of two kinds of materials establishes at least one member bag；
Wherein, the total atom number in each member bag is 500~5000, and the quantity of the member bag is 1~20, described the
One preparatory condition includes：Temperature is 200k~500k, target density is 0.5~1.2g/cm3, structure cell type be preiodic type structure cell.
Preferably, the step S3, including：
Based on a kind of field of force in the Compass field of forces, the PCFF field of forces, the CVFF field of forces, the Universal field of forces, using steepest
Descent method Steepest Descent, conjugate gradient method Conjugate Gradient, Newton method Newton and synthesis Smart
A kind of method in Minimizer carries out energy minimization calculating at least one member bag, obtains and retains minimum energy
Member bag.
Preferably, the step S4, including：
It is pre- second using the one or more in microcanonical assembly NVE, canonical assemblage NVT and isothermal isobaric ensemble NPT
If molecular dynamics optimization is carried out to the member bag of selection under the conditions of, obtains molecular dynamics optimization trace information；
Wherein, second preparatory condition includes：The field of force using the Compass field of forces, the PCFF field of forces, the CVFF field of forces,
One kind in the Universal field of forces, temperature control is using in Velocity scale, Nose, Andersen and Berendsen
One kind, pressure control use one kind in Parrinello, Andersen and Berendsen, and Van der Waals force and Coulomb force use
A kind of method control in Atom Based, Group Based, Ewald, blocking distance is
Preferably, the step S4, in addition to：
Under default pressure, the molecular dynamics of the member bag at a number of different temperatures is obtained, is obtained the multiple
Molecular dynamics optimization trace information under different temperatures；
Wherein, the default pressure is the pressure of target phasor, and the temperature span is described two materials
Freezing point is to boiling point.
Preferably, the step S5, including：
According to the molecular dynamics trace information, between the atom or group selected to same molecule and two kinds of molecules
Radial distribution function RDF between selected atom or group is analyzed respectively, generates RDF curves.
Preferably, the step S5, including：
According to the molecular dynamics trace information under the multiple different temperatures, the minimum member bag of potential energy is obtained, to described
Radial distribution in member bag between same molecule selected atom or group and between atom or group that two kinds of molecules are selected
Function RDF is analyzed respectively, generates RDF curves.
Preferably, the step S6, including：
The first RDF curves between the atom or group selected according to the first molecule, obtain in the first RDF curves the
First atomic distance corresponding to one peak value；
According to the 2nd RDF curves between second molecule selected atom or group, the is obtained in the 2nd RDF curves
Second atomic distance corresponding to one peak value；
According to the 3rd RDF curves between the first molecule and second molecule selected atom or group, described in acquisition
3rd atomic distance corresponding to first peak value in 3rd RDF curves；
Judge the 3rd atomic distance whether be less than or equal to first atomic distance and second atomic distance it
The half of sum, if so, then judge that described two materials dissolve each other under conditions of Current Temperatures and preset ratio, it is otherwise described two
Material is immiscible under conditions of Current Temperatures and preset ratio.
Second aspect, the invention provides a kind of device for judging Binary Liquid liquid intersolubility, described device includes：
Molecular structure generation module, for obtaining the molecular structure of two kinds of materials, and to the molecule knot of described two materials
Structure carries out structure optimization；
Member bag establishes module, is wrapped for described two materials to be established at least one member according to preset ratio；
First optimization module, for carrying out structure optimization at least one member bag, choose the member bag of minimum energy；
Second optimization module, for carrying out molecular dynamics optimization to the member bag of selection；
RDF analysis modules, molecule, atom or group for choosing two kinds of materials in member bag after optimization enter conduct
Analyzed to distribution function RDF；
Judge module, for according to RDF analysis results, judging the intersolubility of described two materials.
As shown from the above technical solution, the present invention obtains the molecular structure of two kinds of materials by computer, by two kinds of materials
Multiple member bags are established by preset ratio, member is wrapped and carries out molecular dynamics optimization, and radial distribution is passed through to the member bag after optimization
Function (RDF) analysis judges Binary Liquid liquid intersolubility, can finally be dissolved each other according to two kinds of liquid of different proportion under different temperatures
Property draw binary liquid-liquid phase figure.In this way, the present invention can be achieved to sentence any two kinds of liquid intersolubilities by computer simulation
It is disconnected and whether equal to obtain the mixed solution in member bag based on the RDF analyses that molecule, atom or group are selected in being wrapped to member
Phase, so as to two kinds of material intersolubilities method can the more directly perceived, intersolubility between two kinds of liquid of reflection exactly, the scope of application
Extensively, simple to operate, equipment requirement is low and result of calculation more accurately and reliably, avoid complex operation in experimentation, flow
It is long, evaporate and cause the problem of such as moieties are poisonous.
Certainly, any product or method for implementing the present invention it is not absolutely required to reach all the above excellent simultaneously
Point.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these figures.
Fig. 1 is a kind of schematic flow sheet of the method for judgement Binary Liquid liquid intersolubility that one embodiment of the invention provides；
Fig. 2 is a kind of schematic flow sheet of the method for calculating binary liquid-liquid phase figure that another embodiment of the present invention provides；
Fig. 3 is the radial distribution function curve of gained in the embodiment of the present invention 1；
Fig. 4 is the radial distribution function curve of gained in the embodiment of the present invention 2；
Fig. 5 is the binary liquid-liquid phase figure of gained in the embodiment of the present invention 3；
Fig. 6 is a kind of structural representation of the device for judgement Binary Liquid liquid intersolubility that one embodiment of the invention provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
Computer Simulation Software used in the embodiment of the present invention is Materials Studio, and involved module has
Visualizer, Dmol 3, Amorphous Cell, Discover etc..The embodiment of the present invention is not limited to this, any to have this
The version of module and function involved by inventive embodiments may be applicable to the present invention.
Fig. 1 is a kind of schematic flow sheet of the method for judgement Binary Liquid liquid intersolubility in one embodiment of the invention, such as Fig. 1
Shown, methods described comprises the following steps：
S1：The molecular structure of two kinds of materials is obtained, and structure optimization is carried out to the molecular structure of described two materials.
Specifically, the molecular structure of two kinds of materials can be drawn using Visualizer, or pass through other software
Such as Chem Draw are imported.Structure optimization is carried out as to the molecule knot of two kinds of materials to the molecular structure of described two materials
Structure carries out energy minimization processing, and Dmol specifically can be selected3In middle Geometry Optimization tasks, Discover
It is one or more of in Minimization tasks to carry out structure optimization.
S2：Described two materials are established at least one member according to preset ratio to wrap.
In this step, when establishing member bag, the molecular number of two kinds of materials is gone out according to preset quality ratiometric conversion, according to molecular number
Ratio establishes member bag.
S3：Structure optimization is carried out at least one member bag, chooses the member bag of minimum energy.
Specifically, member is wrapped and carries out structure optimization, i.e., when carrying out energy minimization calculating to member bag, can be used
Minimization tasks are completed in Discover modules.
S4：Molecular dynamics optimization is carried out to the member bag of selection.
It will be appreciated that molecular dynamics is for the ensemble average in counting statistics mechanics.That is, given at one
Determine in assemblage (such as NVT), the configuration of different-energy is according to certain probability distribution (ANALOGY OF BOLTZMANN DISTRIBUTION), molecular dynamics
It is (and being not only limited to the configuration of minimum energy) to be averaging to all these possible configurations.
In this step, member is wrapped and carries out molecular dynamics simulation optimization, it is exactly that system exists finally make it that system reaches balance
Potential energy level minimum point is nearby vibrated.Specifically, molecular dynamics optimization can use Dynamics in Discover modules to appoint
Business；One or more of combinations in NVE, NVT and NPT assemblage can be used, preferably use NVT assemblages after NPT assemblages annealing.
S5：The molecule, atom or group that two kinds of materials are chosen in member bag after optimization carry out radial distribution function RDF
Analysis.
Specifically, this step selects the molecule of two kinds of materials to carry out radial distribution function RDF analyses, and typical case also may be selected
Atom or group are analyzed；The selection principle of typical atom or group is its geometric position phase in two kinds of material molecules
Together, it can be end group non-hydrogen atom or group, end group hydrogen atom, strand skeletal atom, strand frame center atom etc..Citing
For, RDF analyses use Analysis instruments in Discover modules to carry out
S6：According to RDF analysis results, the intersolubility of described two materials is judged.
Specifically, according to RDF analysis results, judge whether two kinds of materials are homogeneous, if homogeneous state, then two kinds of materials
Dissolve each other, if heterogeneous state, then two kinds of materials are immiscible.
As can be seen here, the present embodiment obtains the molecular structure of two kinds of materials by computer, by two kinds of materials by default ratio
Example establishes multiple member bags, and member is wrapped and carries out molecular dynamics optimization, and passes through radial distribution function (RDF) to the member bag after optimization
Analysis judges Binary Liquid liquid intersolubility, finally can draw binary according to the intersolubility of two kinds of liquid of different proportion under different temperatures
Liquid-liquid phasor.In this way, the present invention is that the judgement to any two kinds of liquid intersolubilities, Er Qieji can be achieved by computer simulation
It is whether homogeneous to obtain the mixed solution in member bag in the RDF analyses that molecule, atom or group are selected in being wrapped to member, so as to two kinds
The method of material intersolubility can it is more directly perceived, exactly reflect two kinds of liquid between intersolubility, it is applied widely, operation letter
Single, equipment requirement is low and result of calculation more accurately and reliably, avoid complex operation in experimentation, long flow path, evaporate
And moieties are poisonous etc. the problem of causing.
In a kind of method for judgement Binary Liquid liquid intersolubility that another embodiment of the present invention provides, as shown in Fig. 2 described
Method also includes the following steps not shown in Fig. 1：
S7：According to the two of the preset ratio kinds of intersolubilities of material at different temperatures, described two things are redefined
The ratio of matter, repeat step S2 to step S6；
S8：According to intersolubility result of described two materials under the conditions of different temperatures and different proportion, generation described two
Binary liquid-liquid phase figure corresponding to kind material.
Specifically, the intersolubility of two kinds of materials of the preset ratio at different temperatures is judged, if in a certain temperature
When, two kinds of materials of preset ratio are immiscible, then redefine the ratio of two kinds of materials, step S2 to S6 read again, to obtain two
Intersolubility result of the kind material under different temperatures and different proportion.In this way, by multiple loop test, existed according to two kinds of materials
Intersolubility result under the conditions of different temperatures and different proportion generates binary liquid-liquid phase figure corresponding to two kinds of materials.
And Binary Liquid liquid phase figure is based on, it directly perceived can must recognize that two kinds of liquid under different proportion different temperatures dissolve each other
Property, can quantify, the more intuitively property of mixed liquor for labeling body.
In step S7, cycle-index is controlled at 5~20 times, and binary liquid-liquid phase figure is generated after preferably 8~12 times.
It will be appreciated that step S1~S6 is identical with step S1~S6 in embodiment illustrated in fig. 1 in the present embodiment, this reality
Example is applied to will not be repeated here.
In the present embodiment, further according under different temperatures two kinds of liquid of different proportion intersolubility draw Binary Liquid-
Liquid phase figure, i.e., the intersolubility and liquid-liquid phasor between any two kinds of liquid are obtained by computer simulation, so as to realize quantitatively,
The property of mixing liquid is more intuitively represented, so as to further direct study and apply.
Specifically, when unformed member bag is established in the step S2, including：
According to default mass ratio, the molecular number of described two materials is obtained, according to described under the first preparatory condition
The molecular number of two kinds of materials establishes at least one member bag；
Wherein, the total atom number in each member bag is 500~5000, and the quantity of the member bag is 1~20, described the
One preparatory condition includes：Temperature is 200k~500k, target density is 0.5~1.2g/cm3, structure cell type be preiodic type structure cell.
Preferably, the total atom number in each member bag is 1500~2000, the quantity (conformation exported of the member bag
Number) it is 6~10, temperature is the freezing point of two kinds of materials to boiling point；Target density is two kinds of material density medians, optimal
Elect the density value being calculated according to the ratio of two kinds of materials as.
Specifically, member is wrapped in the step S3 when carrying out energy minimization calculating (structure optimization), including：
Based on a kind of field of force in the Compass field of forces, the PCFF field of forces, the CVFF field of forces, the Universal field of forces, using steepest
Descent method Steepest Descent, conjugate gradient method Conjugate Gradient, Newton method Newton and synthesis Smart
A kind of method in Minimizer carries out energy minimization calculating at least one member bag, obtains and retains minimum energy
Member bag.
Specifically, when molecular dynamics optimization is carried out in the step S4, including：
It is pre- second using the one or more in microcanonical assembly NVE, canonical assemblage NVT and isothermal isobaric ensemble NPT
If molecular dynamics optimization is carried out to the member bag of selection under the conditions of, obtains molecular dynamics optimization trace information；
Wherein, second preparatory condition includes：The field of force using the Compass field of forces, the PCFF field of forces, the CVFF field of forces,
One kind in the Universal field of forces, temperature control is using in Velocity scale, Nose, Andersen and Berendsen
One kind, pressure control use one kind in Parrinello, Andersen and Berendsen, and Van der Waals force and Coulomb force use
A kind of method control in Atom Based, Group Based, Ewald, blocking distance is
Preferably, after being made annealing treatment using NPT assemblages, using NVT assemblages, the member of selection is wrapped under the second preparatory condition
Molecular dynamics optimization is carried out, obtains molecular dynamics optimization trace information.
For example, when obtaining molecular dynamics optimization trace information：Time step is 1fs, amount to evaluation time be 3~
1000ps, preferably 20~500ps；And a frame data are exported every 30~1000 steps, to obtain molecular dynamics optimization track letter
Breath.
Further, the step S4, in addition to：
Under default pressure, the molecular dynamics of the member bag at a number of different temperatures is obtained, is obtained the multiple
Molecular dynamics optimization trace information under different temperatures；
Wherein, the default pressure is the pressure of target phasor, and the temperature span is described two materials
Freezing point is to boiling point.
For example, liquid-liquid phasor under normal pressure need to be such as calculated, then pressure is arranged to 0.0001GPa, and temperature setting is two kinds
The freezing point of material calculates the molecular dynamics of first pack arrangement under 1~8 different temperatures between boiling point.
Specifically, analysis obtains a kind of embodiment of RDF curves in the step S5, including：
According to the molecular dynamics trace information, between the atom or group selected to same molecule and two kinds of molecules
Radial distribution function RDF between selected atom or group is analyzed respectively, generates RDF curves.
Alternatively, analysis obtains the another embodiment of RDF curves in the step S5, including：
According to the molecular dynamics trace information under the multiple different temperatures, the minimum member bag of potential energy is obtained, to described
Radial distribution in member bag between same molecule selected atom or group and between atom or group that two kinds of molecules are selected
Function RDF is analyzed respectively, generates RDF curves.
Wherein, each member includes the molecule of two kinds of materials：The first molecule and second of molecule；Then same molecule choosing
Radial distribution function RDF between fixed atom or group and between atom or group that two kinds of molecules are selected is specifically included：The
A kind of radial distribution function RDF between molecule selected atom or group；Footpath between second of molecule selected atom or group
To distribution function RDF；And between the selected atom of the first molecule or group and the selected atom or group of second of molecule
Radial distribution function RDF.
Further, the step S6, specifically comprises the following steps：
S61：The first RDF curves between the atom or group selected according to the first molecule, obtain the first RDF curves
In the first atomic distance corresponding to first peak value；
S62：According to the 2nd RDF curves between second of molecule selected atom or group, the 2nd RDF curves are obtained
In the second atomic distance corresponding to first peak value；
S63：According to the 3rd RDF curves between the first molecule and second of molecule selected atom or group, obtain
3rd atomic distance corresponding to first peak value in the 3rd RDF curves；
S64：Judge whether the 3rd atomic distance is less than or equal to first atomic distance and second atomic distance
From the half of sum, if so, then judge that described two materials dissolve each other under conditions of Current Temperatures and preset ratio, it is otherwise described
Two kinds of materials are immiscible under conditions of Current Temperatures and preset ratio.
As can be seen here, if the 3rd atomic distance is less than or equal to first atomic distance and second atomic distance
The half of sum, then two kinds of liquid are homogeneous under conditions of the Current Temperatures and preset ratio, then two components are mutual under this condition
Molten, otherwise two kinds of liquid are heterogeneous state under conditions of the Current Temperatures and preset ratio, then two components are immiscible.
In summary, the embodiment of the present invention achieves following good effect or advantage：
It is applied widely, it can be used for the liquid-liquid phasor for judging any two kinds of materials；This method can also extend to simultaneously
The calculating of liquid-liquid phasor under high pressure or lower pressure, solve sectional interest or condition experiment cost is high or condition difficulty reaches
The problem of；It is simple to operate, equipment requirement is low, can complete on a common computer, avoid complex operation in experimentation, stream
Journey is long, evaporates, the problems such as moieties are poisonous；Compared with the GEMC methods of prior art, result of calculation is more accurate, can
Lean on.
In order to illustrate more clearly of technical scheme, several specific embodiments are provided below to describe in detail.
Embodiment 1
Judge acetic acid with water quality ratio for 1:Intersolubility of 1 system under the conditions of 25 DEG C, 100kPa：
1) hydrone and molecular acid are drawn using Visualizer and uses Dmol3Geometry in module
Its structure of Optimization task optimizations.
2) Construction task creations member bag, hydrone and molecular acid in Amorphous Cell modules are used
Number is respectively 366 and 110 (total atom numbers 1978), exports 6 conformations, temperature setting 298K, and target density is
1.024g/cm3, structure cell type selecting periodicity structure cell, the Compass field of forces are selected in the field of force.
3) Minimization tasks Smart Minimizer methods in Discover modules are used to carry out 6 member bags
Energy minimization is calculated, and from the Compass field of forces, the member for retaining minimum energy is wrapped.
4) molecular dynamics optimization is carried out using NPT assemblages, after annealing, is calculated using NVT assemblages, temperature is
298K, pressure 0.0001GP, using Andersen method of temperature-control by, Berendsen pressure control methods, Van der Waals force and Coulomb force selection
Atom Based methods, block distance and are set asTime step is 1fs, and total evaluation time is 20ps, is exported every 100 steps
One frame data, obtain molecular dynamics optimization trail file.
5) the upper oxygen atoms of-OH in oxygen atom and acetic acid are selected in hydrone, RDF analyses are carried out to trail file, obtained
In molecular acid between oxygen atom, in hydrone between oxygen atom and in acetic acid between oxygen atom and water oxygen atom
Radial distribution function RDF (rOa-Oa)、RDF(rOw-Ow) and RDF (rOa-Ow), as a result see Fig. 3, radially divide in three curves
Value corresponding to first peak-to-peak value of cloth function is respectively rOa-Ow, peak<(rOa-Oa, peak+rOw-Ow, peak)/2, therefore judge acetic acid with water quality ratio for 1:1 body
Tie up to 25 DEG C, dissolve each other under the conditions of 100kPa, be homogeneous state.
Embodiment 2
Judge n-hexane with water quality ratio for 1:Intersolubility of 1 system under the conditions of 50 DEG C, 100kPa.
1) n-hexane molecule and hydrone are drawn using Visualizer and uses Dmol3Geometry in module
Its structure of Optimization task optimizations.
2) the use of 57 n-hexane molecules and 266 hydrones (total atom number 1938), setting initial density is 0.845g/
cm3Member bag is established, exports 6 conformations, temperature setting 323K, structure cell type selecting periodicity structure cell, Compass is selected in the field of force
The field of force.
3) energy minimization calculating is carried out to 6 member bags, from the Compass field of forces, the member for retaining minimum energy is wrapped.
4) molecular dynamics optimization is carried out using NPT assemblages, after annealing, is calculated using NVT assemblages, temperature is
323K, pressure 0.0001GP, using Andersen method of temperature-control by, Berendsen pressure control methods, Van der Waals force and Coulomb force selection
Atom Based methods, block distance and are set asTime step is 1fs, and total evaluation time is 20ps, is exported every 100 steps
One frame data, obtain molecular dynamics optimization trail file.
5) from the end carbon atom of n-hexane one and hydrone analysis radial distribution function, RDF (r are obtainedC1-C1)、RDF
(rOw-Ow) and RDF (rC1-Ow) curve, see Fig. 4, the value difference in three curves corresponding to first peak-to-peak value of radial distribution function
For rC1-Ow, peak>
(rC1-C1, peak+rOw-Ow, peak)/2, therefore judge n-hexane with water quality ratio for 1:1 system is not mutual under the conditions of 50 DEG C, 100kPa
It is molten, be heterogeneous state.
Embodiment 3
Calculate n-butanol/water system liquid-liquid phasor under 100kPa.
I, n-butanol mass fraction 50% (25 DEG C) in mixture：80 n-butanol molecules and 329 hydrone (total atoms
Number 2187), initial density 0.9039g/cm3 establish member bag, other calculation procedures such as embodiment 1, use oxygen atom in n-butanol
RDF analyses are carried out with water oxygen atom, are judged under 298K, the ratio is immiscible.
N-butanol mass fraction 30% (25 DEG C) in II, mixture：50 n-butanol molecules and 479 hydrones are (total former
Subnumber 2187), initial density 0.9415g/cm3 establish member bag, other calculation procedures such as I, judge that the ratio is immiscible under 298K.
N-butanol mass fraction 10% (25 DEG C) in III, mixture：17 n-butanol molecules and 692 hydrones are (total former
Subnumber 2142), initial density 0.9792g/cm3 establish member bag, other calculation procedures such as I, judge that the ratio is immiscible under 298K.
N-butanol mass fraction 5% (25 DEG C) in IV, mixture：8 n-butanol molecules and 624 hydrone (total atoms
Number 1992), initial density 0.9886g/cm3 establish member bag, other calculation procedures such as I, judge that the ratio is dissolved each other under 298K.
V, n-butanol mass fraction 10% (45 DEG C) in mixture：It will obtain making after trail file carries out NPT assemblages in III
Dynamics calculation is carried out with NVT assemblages, temperature setting 318K, judges that the ratio is immiscible under 318K.
N-butanol mass fraction 5% (45 DEG C) in VI, mixture：It will obtain making after trail file carries out NPT assemblages in IV
Dynamics calculation is carried out with NVT assemblages, temperature setting 318K, judges that the ratio is dissolved each other under 318K.
N-butanol mass fraction 10% (65 DEG C) in VII, mixture：It will obtain making after trail file carries out NPT assemblages in V
Dynamics calculation is carried out with NVT assemblages, temperature setting 338K, judges that the ratio is immiscible under 338K.
N-butanol mass fraction 5% (65 DEG C) in VIII, mixture：After trail file progress NPT assemblages will be obtained in VI
Dynamics calculation is carried out using NVT assemblages, temperature setting 338K, judges that the ratio is dissolved each other under 338K.
N-butanol mass fraction 10% (85 DEG C) in IX, mixture：After trail file progress NPT assemblages will be obtained in VII
Dynamics calculation is carried out using NVT assemblages, temperature setting 358K, judges that the ratio is immiscible under 358K.
X, n-butanol mass fraction 5% (85 DEG C) in mixture：It will obtain making after trail file carries out NPT assemblages in VIII
Dynamics calculation is carried out with NVT assemblages, temperature setting 358K, judges that the ratio is dissolved each other under 358K.
N-butanol mass fraction 10% (5 DEG C) in XI, mixture：It will obtain making after trail file carries out NPT assemblages in III
Dynamics calculation is carried out with NVT assemblages, temperature setting 278K, judges that the ratio is immiscible under 278K.
N-butanol mass fraction 5% (5 DEG C) in XII, mixture：It will obtain making after trail file carries out NPT assemblages in IV
Dynamics calculation is carried out with NVT assemblages, temperature setting 278K, judges that the ratio is dissolved each other under 278K.
N-butanol mass fraction 70% (25 DEG C) in XIII, mixture：114 n-butanol molecules and 201 hydrones are (total
Atomicity 2313), initial density 0.8663g/cm3 establish member bag, other calculation procedures such as I, judge that the ratio is not mutual under 298K
It is molten.
N-butanol mass fraction 90% (25 DEG C) in XIV, mixture：131 n-butanol molecules and 60 hydrones are (total former
Subnumber 2145), initial density 0.8287g/cm3 establish member bag, other calculation procedures such as I, judge that the ratio is dissolved each other under 298K.
N-butanol mass fraction 80% (25 DEG C) in XV, mixture：116 n-butanol molecules and 119 hydrones are (total former
Subnumber 2097), initial density 0.8474g/cm3 establish member bag, other calculation procedures such as I, judge that the ratio is dissolved each other under 298K.
N-butanol mass fraction 75% (25 DEG C) in XVI, mixture：115 n-butanol molecules and 158 hydrones are (total
Atomicity 2199), initial density 0.8569g/cm3 establish member bag, other calculation procedures such as I, judge that the ratio is not mutual under 298K
It is molten.
N-butanol mass fraction 75% (45 DEG C) in XVII, mixture：Trail file will be obtained in XVI and carries out NPT assemblages
Dynamics calculation is carried out using NVT assemblages afterwards, temperature setting 318K, judges that the ratio is immiscible under 318K.
N-butanol mass fraction 80% (45 DEG C) in XVIII, mixture：Trail file will be obtained in XV and carries out NPT assemblages
Dynamics calculation is carried out using NVT assemblages afterwards, temperature setting 318K, judges that the ratio is dissolved each other under 318K.
N-butanol mass fraction 75% (65 DEG C) in XIX, mixture：Trail file will be obtained in XVII and carries out NPT assemblages
Dynamics calculation is carried out using NVT assemblages afterwards, temperature setting 338K, judges that the ratio is immiscible under 338K.
N-butanol mass fraction 80% (65 DEG C) in XX, mixture：Trail file will be obtained in XVIII and carries out NPT assemblages
Dynamics calculation is carried out using NVT assemblages afterwards, temperature setting 338K, judges that the ratio is dissolved each other under 338K.
N-butanol mass fraction 75% (85 DEG C) in XXI, mixture：After trail file progress NPT assemblages will be obtained in XIX
Dynamics calculation is carried out using NVT assemblages, temperature setting 358K, judges that the ratio is dissolved each other under 358K.
N-butanol mass fraction 70% (85 DEG C) in XXII, mixture：Trail file will be obtained in VIII and carries out NPT assemblages
Dynamics calculation is carried out using NVT assemblages afterwards, temperature setting 358K, judges that the ratio is immiscible under 358K.
N-butanol mass fraction 80% (5 DEG C) in XXIII, mixture：After trail file progress NPT assemblages will be obtained in XV
Dynamics calculation is carried out using NVT assemblages, temperature setting 278K, judges that the ratio is immiscible under 278K.
N-butanol mass fraction 85% (5 DEG C) in XXIV, mixture：121 n-butanol molecules and 88 hydrones are (total former
Subnumber 2079), initial density 0.8381g/cm3 establish member bag, after annealing, NPT assemblages and NVT assemblages carry out dynamics meter
Temperature is arranged to 278K in calculation, other same I, judges that the ratio is dissolved each other under 278K.
By I-XXIV results drafting n-butanol-water liquid liquid phase figure, and with《Solvent handbook》Middle n-butanol solubility in water
Compare, see Fig. 5, it is seen that the method using computer Simulation calculation binary liquid-liquid phase figure involved by the embodiment of the present invention is accurate,
Reliably.
Fig. 6 is a kind of structural representation of the device for judgement Binary Liquid liquid intersolubility that one embodiment of the invention provides, such as
Shown in Fig. 6, described device includes：Molecular structure generation module 601, member bag establish module 602, the first optimization module 603, second
Optimization module 604, RDF analysis modules 605 and judge module 606.
Molecular structure generation module 601, for obtaining the molecular structure of two kinds of materials, and to the molecule of described two materials
Structure carries out structure optimization；
Member bag establishes module 602, is wrapped for described two materials to be established at least one member according to preset ratio；
First optimization module 603, for carrying out structure optimization at least one member bag, choose the member of minimum energy
Bag；
Second optimization module 604, for carrying out molecular dynamics optimization to the member bag of selection；
RDF analysis modules 605, molecule, atom or group for choosing two kinds of materials in member bag after optimization enter
Row radial distribution function RDF is analyzed；
Judge module 606, for according to RDF analysis results, judging the intersolubility of described two materials.
It should be noted that the device for judging Binary Liquid liquid intersolubility in the present embodiment can be located in computer, with reality
Existing computer simulation judges Binary Liquid liquid intersolubility, and binary liquid-liquid phase figure is further calculated.
For device embodiment, because it is substantially similar to embodiment of the method, so description is fairly simple, it is related
Part illustrates referring to the part of device embodiment.
In the description of the invention, it is necessary to which the orientation of the instruction such as explanation, term " on ", " under " or position relationship are base
In orientation shown in the drawings or position relationship, description description of the invention and simplified, rather than instruction or hint are for only for ease of
Signified device or element must have specific orientation, with specific azimuth configuration and operation, therefore it is not intended that to this
The limitation of invention.Unless otherwise clearly defined and limited, term " installation ", " connected ", " connection " should be interpreted broadly, example
Such as, can be fixedly connected or be detachably connected, or be integrally connected；Can mechanically connect or be electrically connected
Connect；Can be joined directly together, can also be indirectly connected by intermediary, can be the connection of two element internals.For this
For the those of ordinary skill in field, the concrete meaning of above-mentioned term in the present invention can be understood as the case may be.
It should also be noted that, herein, such as first and second or the like relational terms are used merely to one
Entity or operation make a distinction with another entity or operation, and not necessarily require or imply between these entities or operation
Any this actual relation or order be present.Moreover, term " comprising ", "comprising" or its any other variant are intended to contain
Lid nonexcludability includes, so that process, method, article or equipment including a series of elements not only will including those
Element, but also the other element including being not expressly set out, or it is this process, method, article or equipment also to include
Intrinsic key element.In the absence of more restrictions, the key element limited by sentence "including a ...", it is not excluded that
Other identical element also be present in process, method, article or equipment including the key element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
- A kind of 1. method for judging Binary Liquid liquid intersolubility, it is characterised in that methods described includes：S1：The molecular structure of two kinds of materials is obtained, and structure optimization is carried out to the molecular structure of described two materials；S2：Described two materials are established at least one member according to preset ratio to wrap；S3：Structure optimization is carried out at least one member bag, chooses the member bag of minimum energy；S4：Molecular dynamics optimization is carried out to the member bag of selection；S5：The molecule, atom or group that two kinds of materials are chosen in member bag after optimization carry out RDF points of radial distribution function Analysis；S6：According to RDF analysis results, the intersolubility of described two materials is judged.
- 2. according to the method for claim 1, it is characterised in that methods described also includes：S7：According to the two of the preset ratio kinds of intersolubilities of material at different temperatures, described two materials are redefined Ratio, repeat step S2 to step S6；S8：According to intersolubility result of described two materials under the conditions of different temperatures and different proportion, described two things are generated Binary liquid-liquid phase figure corresponding to matter.
- 3. according to the method for claim 1, it is characterised in that the step S2, including：According to default mass ratio, the molecular number of described two materials is obtained, according to described two under the first preparatory condition The molecular number of material establishes at least one member bag；Wherein, the total atom number in each member bag is 500~5000, and the quantity of the member bag is 1~20, and described first is pre- If condition includes：Temperature is 200k~500k, target density is 0.5~1.2g/cm3, structure cell type be preiodic type structure cell.
- 4. according to the method for claim 1, it is characterised in that the step S3, including：Based on a kind of field of force in the Compass field of forces, the PCFF field of forces, the CVFF field of forces, the Universal field of forces, declined using steepest Method Steepest Descent, conjugate gradient method Conjugate Gradient, Newton method Newton and synthesis Smart A kind of method in Minimizer carries out energy minimization calculating at least one member bag, obtains and retains minimum energy Member bag.
- 5. according to the method for claim 1, it is characterised in that the step S4, including：Using the one or more in microcanonical assembly NVE, canonical assemblage NVT and isothermal isobaric ensemble NPT, in the second default bar Molecular dynamics optimization is carried out to the member bag of selection under part, obtains molecular dynamics optimization trace information；Wherein, second preparatory condition includes：The field of force is using the Compass field of forces, the PCFF field of forces, the CVFF field of forces, Universal One kind in the field of force, temperature control is using one kind in Velocity scale, Nose, Andersen and Berendsen, pressure Control uses one kind in Parrinello, Andersen and Berendsen, and Van der Waals force and Coulomb force use Atom A kind of method control in Based, Group Based, Ewald, blocking distance is。
- 6. according to the method for claim 1, it is characterised in that the step S4, in addition to：Under default pressure, the molecular dynamics of the member bag at a number of different temperatures is obtained, obtains the multiple difference At a temperature of molecular dynamics optimization trace information；Wherein, the default pressure is the pressure of target phasor, and the temperature span is the solidification of described two materials Put to boiling point.
- 7. according to the method for claim 5, it is characterised in that the step S5, including：According to the molecular dynamics optimize trace information, to same molecule select atom or group between and two kinds of molecules Radial distribution function RDF between selected atom or group is analyzed respectively, generates RDF curves.
- 8. according to the method for claim 5, it is characterised in that the step S5, including：Trace information is optimized according to the molecular dynamics, obtains the minimum member bag of potential energy, to same molecule in the member bag Radial distribution function RDF between selected atom or group and between atom or group that two kinds of molecules are selected is divided respectively Analysis, generate RDF curves.
- 9. the method according to claim 7 or 8, it is characterised in that the step S6, including：The first RDF curves between the atom or group selected according to the first molecule, first is obtained in the first RDF curves First atomic distance corresponding to peak value；According to the 2nd RDF curves between second of molecule selected atom or group, first is obtained in the 2nd RDF curves Second atomic distance corresponding to peak value；According to the 3rd RDF curves between the first molecule and second of molecule selected atom or group, the described 3rd is obtained 3rd atomic distance corresponding to first peak value in RDF curves；Judge whether the 3rd atomic distance is less than or equal to first atomic distance and the second atomic distance sum Half, if so, then judge that described two materials dissolve each other under conditions of Current Temperatures and preset ratio, otherwise described two materials It is immiscible under conditions of Current Temperatures and preset ratio.
- 10. a kind of device for judging Binary Liquid liquid intersolubility, it is characterised in that described device includes：Molecular structure generation module, for obtaining the molecular structure of two kinds of materials, and the molecular structure of described two materials is entered Row structure optimization；Member bag establishes module, is wrapped for described two materials to be established at least one member according to preset ratio；First optimization module, for carrying out structure optimization at least one member bag, choose the member bag of minimum energy；Second optimization module, for carrying out molecular dynamics optimization to the member bag of selection；RDF analysis modules, molecule, atom or group for choosing two kinds of materials in member bag after optimization carry out radial direction point Cloth function RDF is analyzed；Judge module, for according to RDF analysis results, judging the intersolubility of described two materials.
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