Fullprof软件使用手册：粉末衍射分析详解

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"Fullprof手册——一份详尽的粉末衍射分析软件使用指南" "Fullprof手册"是一份针对粉末衍射分析软件FullProf的详细使用教程，由Juan Rodríguez-Carvajal编著，他在CEA-CNRS的Léon Brillouin实验室工作。该手册旨在为用户提供全面的操作指导，尽管它仍在不断完善中，作者也承认其中可能存在的错误。FullProf是一款在晶体学、磁学、衍射物理和数据分析领域具有广泛应用的软件。手册的核心部分涵盖了CODFIL.pcr这个主要控制文件的详细解释，这是一个关键的配置文件，用于设定和控制FullProf的各项功能。此外，文档的大量篇幅专门用来解析实例和处理特定问题，这有助于用户理解和解决实际工作中遇到的复杂情况。对于初学者来说，虽然需要具备一定的晶体学、磁学和衍射物理的基础知识，才能更好地使用FullProf，但手册中的实例和专题讨论能帮助他们逐步上手。即使是有经验的专家，在初次或反复使用FullProf时也可能面临挑战。因此，为了使软件更易于使用，开发团队正在不断努力。特别提到了"FullProf2000"的新版本，它专为Windows 9x/2k/NT操作系统设计，与WinPLOTR一同提供，形成了一个现代且用户友好的应用环境。未来还计划为Linux系统开发WinPLOTR的版本，以满足不同平台用户的需求。 FullProf软件的主要功能可能包括但不限于数据处理、粉末衍射模式的模拟和解析、晶体结构的精修以及磁结构的分析等。它能帮助研究人员处理实验数据，进行结构解析，从而在材料科学、地质学、化学和其他相关领域进行深入研究。手册的详细内容将覆盖这些功能的使用步骤、参数设置以及结果解读，是学习和使用FullProf的宝贵资源。

• If you experience difficulties from the very beginning (for instance a singular matrix at the first

refinement), start refining the scale factors only and examine the difference pattern with a plotting

program. These will most of the time reveal a glaring blunder in the input data (zero-shift, step size,

angular limits etc).

• Owing to the complexity of the control file, error messages from the program are not always easy to

decipher in that they do not necessarily point to the initial error but merely to one of its

consequences. Most of the times, run time errors result from an error in the sequence of lines in the

control file, e.g., an inadequacy between the number of atoms stated on line 19 and the number of

atomic positions given on lines lines 25.

Examples. Content of pcr_dat.zip

To test the installation of the program, or for training purposes, a list of complete examples are provided

together with FullProf. The file pcr_dat.zip can be obtained by anonymous ftp to the server

charybde.saclay.cea.fr in the same area as the program. Set the mode to binary in order to get properly

the file. The file pcr_dat.zip must be unzipped using PKWARE pkzip/pkunzip or WinZip. The resulting

ASCII files are in PC/DOS format. They have to be converted to UNIX, Mac, or VMS using one of the

appropriate utilities (dos2unix, editor...).

The files contained in pcr_dat.zip can be used for testing FullProf. They have been selected in order to

illustrate the use of FullProf in a variety of situations. In no way the proposed models pretend to be the

most adequate to the data. In some cases there is a clear disagreement between the data and the model.

The user may try to improve the models including new parameters that have a clear physical relevance.

Increasing the number of parameters just for getting more nice fits may result in non sense values.

For a quit test under DOS or under UNIX the user can type at the command line:

fullprof_alias < tempo.inp

FullProf will be executed for all files existing in file: tempo.inp where the answers expected by

the program are collected.

In a Windows 9x/2k/NT environment the user may execute the file test_fp.bat to run all examples.

Verify first that the DOS-like version fp2k.exe is in a proper directory within the PATH environment

variable. The Windows version of FullProf is not adequate for rapid tests because the program needs the

intervention of the user to answer questions about the continuation or stop the refinement process.

The number and nature of files within file pcr_dat.zip may change with different releases.

At present the files are:

PCR Code Purpose Data File

Ce1 refinement of a CeO

standard ceo2.dat

Ce2 " "

Rutana Conventional X-ray diffraction pattern: Rutile+Anatase Rutana.dat

Tbbaco Conventional X-ray diffraction pattern: Tb

BaCoO

Tbbaco.dat

Tbba Conventional X-ray diffraction pattern: Profile Matching "

Tb Search for Tb,Ba and Co by Montecarlo with prev. output Tb.int

PbSOx Crystal structure refinement of PbSO

with X-rays Pbsox.dat

PbSO Profile matching to obtain an overlapped intensity file "

PbSOm Search for Pb by Montecarlo using previous output pbsom.int

Pb Profile matching test of PbSO4 neutron data Pbso4.dat

PbSO4 Crystal structure refinement of PbSO

PbSO4a Crystal structure refinement of PbSO

(anisotropic b's) "

Pb_ho Artificial multipattern refinement Pbso4.dat,Pbsox.dat,

Hobk.dat

Pb_sing Example of new format of PCR file adapted for multipattern

refinements

Pbso4.dat

Pb_san Example of Simulated Annealing: solves the structure of PbSO

Pb_san.int

C60s Compares C

x-tal data to form-factor SPHS sin(Qr)/Qr C60.int

C60 Refinement of C

x-tal data using symmetry adapted cubic

harmonics. Form-factor type SASH.

C60.int

Dy Four different ways of refining the crystal Dy.dat

Dya and magnetic structure of DyMn

Dyb "

Dyc "

Hocu Refinement of the magnetic structure of Ho

(D1B data) Hocu.dat

Hobb Refinement with integrated intensities (Nuc+mag) Hobb.int

Hob Montecarlo search for mag. moments in Ho2BaNiO5 "

Hobk1 Three different ways of refining the crystal Hobk.dat

Hobk2 and magnetic structure of Ho2BaNiO5 "

Hobk3 "

Cuf1k Refinement of crystal & magnetic structrure of CuF

Microstructural effects (D1A data)

Cuf1k.dat

Pb_san Example of Simulated Annealing: solves the structure of PbSO

Pb_san.int

La Two ways for strain refinement in La

NiO

(D1B) La.dat

Lab with low resolution neutron powder data "

Monte Montecarlo test with single crystal data Monte.int

Hmt Rigid body-TLS refinement of published single X-tal data Hmt.int

Urea Test Rigid body with satellites (simulated data) Urea.dat

Pyr Test Rigid body with general TLS refinement (sim. data) Pyr.dat

Ycbacu YBaCuO with Ca. Data from D1A Ycbacu.dat

Arg_si Corrected TOF data of Si from SEPD at Argonne Arg_si.dat

Cecoal TOF data from POLARIS at ISIS Cecoal

Cecua1 TOF data from POLARIS at ISIS Cecua1.dat

Lamn_3t2 Constant wavelenght neutron data from 3T2 (LLB) of LaMnO

Lamn_3t2.dat

Lamn_pol TOF data from POLARIS at ISIS on the RT phase of LaMnO

Lamn_pol.dat

Si3n4r Quantitative phase analysis. Two polymorphs of Si

. (Studvik) Si3n4r.dat

Sin_3t2 As above but data taken at 3T2 (LLB) Sin_3t2

Pb_san Example of Simulated Annealing: solves the structure of PbSO

Pb_san.int

Maghem Refinement of Fe

-Fe

at RT (D1A data) Maghem

In general, the user must first run the program to verify that the provided pcr-files behave correctly. After

that, the user should make a copy of the control files for saving them before running his(her) own options.

The best way is to modify the given values for different sets of parameters and run the program. The

beginner must make extensive use of editor-plot cycles. The plot of the file CODFIL.prf is of absolutely

necessity for knowing the behaviour of the program under bad (or inaccurate) input parameters.

To use the above files for training, the inexperienced user must start with the simplest cases, that is

ce1.pcr and ce2.pcr used to process the file ceo2.dat. This file corresponds to a data collection on cerium

oxide with a laboratory X-ray powder diffractometer, using CuK

doublets. Other simple examples with

conventional X-rays are: the Rutile-Anatase mixture, that allow a quantitative analysis of the relative

fraction of each component, and the diffraction pattern of Tb

BaCoO

presenting micro-absorption effects

that produce some negative temperature factors. The user can modify the input file in order to input the

micro-absorption correction and look for the changes in the results. The next files to be processed are

those of PbSO

. The data file correspond to a laboratory X-ray diffraction pattern (pbsox.dat) and to a

neutron powder diffraction pattern (pbso4.dat) obtained on D1A (ILL) that was used in a Round Robin

on Rietveld refinement (R.J. Hill (1992), J.Appl.Cryst 25, 589). For a person working mainly with crystal

structures the next files to be studied are: ycbacu, hmt and urea for powder diffraction.

Some files to be used with single crystal data are also given: c60. The first one uses a simplistic model

(just a spherical shell) for describing the C

molecule that gives relatively good results. The user can try

this file as an example of special form factor refinement. The free parameter is the radius of the C

molecule. The file monte corresponds to an artificial use of the Montecarlo technique for searching a

starting set of initial parameters. Data are from neutron diffraction on a single crystal of oxidised

NiO

4+δ

People interested in magnetic structures may use the rest of the files in the following order.

• la, lab: refinement of the low temperature phase crystal and magnetic structure of La

NiO

. The

data are from a medium-low resolution neutron powder diffractometer (D1B at ILL). This phase

present a microstrain that is refined using two equivalent methods in the two files. The magnetic

structure is very simple. A peak from an impurity phase is near the first magnetic peak.

• The files hobb, hob, hobk1, hobk2, hobk3 concern the refinement of the crystal and magnetic

structures of Ho

BaNiO

at 1.5K, using different methods and conditions. The user can verify

that hob.pcr can solve the magnetic structure of Ho

BaNiO

just testing random configurations.

This is a very favourable case and this method cannot be applied for general magnetic structure

determination. The data are from D1B at ILL.

• Hocu: refinement of the magnetic structure of Ho

. The data have been taken on D1B

diffractometer at the ILL. Magnetic scattering dominates nuclear scattering. The crystal structure

cannot be refined with these data.

• Cuf1k: refinement of the magnetic structure of CuF

. The data have been taken on D1A

diffractometer when it was installed provisionally at the LLB. Nuclear scattering dominates

magnetic scattering. The diffraction pattern cannot be refined properly without taking into

account microstructural effects.

• The files dy, dya, dyb, dyc use different methods to refine the incommensurate magnetic

structure of DyMn

. This is a conical structure that can be refined using a real space

approach as in dy and dya or using Fourier components of the magnetic moments, which is the

general formalism of FullProf for handling magnetic structures. This is the case of files dyb and

dyc.

An example of simulated annealing application is given. The file is Pb_san.pcr, where the user finds a

particular case of how to prepare a PCR file adapted for simulated annealing. The user may play with the

different parameters (starting temperature, number of Montecarlo cycles per temperature, type of

algorithm, number of reflections to be used, etc) to experience when the method is able to solve the

PbSO

structure.

The only right way to learn about crystal and magnetic structure refinements is practising with real

data as these are. However, it is better when the user try with its own data on a problem of interest to

him(her).

ADDITIONAL NOTES

Magnetic Refinements

For a commensurate structure two descriptions of the magnetic structure are possible: the general

formalism using Fourier components of magnetic moments through the propagation vectors or a

crystallographic-like description using the magnetic unit cell. The simplest one, for a non-expert user, is

to describe the magnetic structure in the magnetic unit cell. In that case the following important points

must be taken into account:

• For magnetic structures described in a magnetic unit cell larger than the crystallographic cell, the co-

ordinates of atoms must be changed consequently, as well as the unit cell parameters. The codes for

common (or related) parameter with the crystallographic counterpart must be changed applying the

correct multiplier factor. It is worth stressing that codes for cell parameters are actually applied to the

"cell constants" (A, B, C, D, E, F) defined by the expression:

1/d

= A h

+ B k

+ C l

+ D kl + E hl + F hk

Therefore, if you are dealing with an orthorhombic structure which has a magnetic structure with

propagation vector k=(1/2, 0, 0) you have to use the magnetic unit cell 2×a, b, c and if the codes of the

crystallographic unit cell a,b,c are for example:

Cell a b c 90 90 90

CodeCell 81.00 91.00 101.00 0 0 0

the corresponding values for the magnetic counterpart are:

Cell 2a b c 90 90 90

CodeCell 80.25 91.00 101.00 0 0 0

The reason is that the crystallographic cell constant A is in this case: A

=1/a

and the magnetic cell

constant is A

=1/(2a)

= 0.25A

. As explained above, the multiplier factor is applied to shifts of

parameters.

• The scale factors of the crystallographic and magnetic parts have to be related in some way in order

to get good values of magnetic moments. This relation depends on the way the users describes the

magnetic structure, however several rules can be useful to avoid bulk errors:

1. Use the correct occupation numbers in the crystallographic part (=multiplicity of special

position/general multiplicity)

2. The number of magnetic atoms in the chemical unit cell must coincide with the description above,

therefore the occupation numbers in the magnetic part are related to the number of symmetry

operators given and the centrosymmetry (or not) of the magnetic structure.

If these requirements are satisfied and the magnetic unit cell is the same as the chemical one, the scale

factors are strictly the same numbers; and, therefore represent the same parameter with a shift equal to

unity. If the magnetic unit cell is a multiple one, and the above requirements are satisfied, the relation

between the scale factors is a multiplier factor relating the two scale factors given by:

= 1.0/(V

)

=(V

)

Where S

is the crystallographic scale factor and S

the magnetic scale factor. In the case of large

magnetic cells it can be more convenient to modify the occupation numbers of magnetic atoms in such a

way that the two scale factors coincide.

For incommensurate magnetic structures the general formalism must be applied. When the magnetic

structure is described using the formalism of propagation vectors, the components M

, M

no longer

represent true magnetic moments (see mathematical section). The user should be cautious in interpreting

the output files. The modulus of the "magnetic moment" represents the Fourier component modulus of an

atomic magnetic moment which have to be calculated externally. The calculation of the intensity is based

on the expression of magnetic structure factor given in mathematical section; therefore the user knows

how to play with his input items in order to obtain physically sound results.

For the spherical description of the magnetic moments the following must be taken into account:

• The orthonormal system with respect to which are defined the spherical angles verifies:

X axis coincides with the crystallographic a-axis

Y axis belongs to the plane a-b

Z-axis is perpendicular to the plane a-b

The particular implementation of spherical components in magnetic structure refinements is that the Z-

axis must coincide with c. This works in all crystallographic systems except for triclinic. The monoclinic

setting must be changed to the setting 1 1 2/m to satisfy the above prescription.

Propagation vectors

A complete list of reflections can be generated when propagation vectors of an incommensurate structure

are present. To each fundamental reflection it is added the corresponding satellites. For n propagation

vectors k

, k

,... k

, there are n satellites obtained from each fundamental reciprocal lattice vector h:

Fundamental reflection: h = (h, k, l)

Satellites h

=h+ k

, h

=h+ k

,... h

=h+ k

In the present version of the program no symmetry analysis is performed. We recommend to use the

triclinic space group of symbol L -1 (where L = P, A, B, C, F, I, R) in order to have a full set of reflections

with the proper multiplicity when the true magnetic symmetry is not known.

The program generates first a list of unique reflections corresponding to the required space group and

then adds the satellites. This method had to be modified for reflections belonging to the boundary planes

and lines of the asymmetric region of the reciprocal space in order to obtain the correct number of

reflections and not miss (or repeat) some of them. Be careful with propagation vectors k equivalent to -k!

Two vectors k

and k

are "equivalent" if k

-k

is a vector of the reciprocal lattice. So, for k

≡-k

, if

H=2k

belongs to the reciprocal lattice, k

is single and belongs to a point of high symmetry of the

Brillouin Zone. In such cases only ONE propagation vectors should be introduced

Nvk

=1, if the user puts

Nvk

=-1, the satellite reflections are not correctly generated.

For centred cells a propagation vector k having components ±1/2, verifies that 2k has integer

components, but that does not mean that k and -k are equivalent, because 2k could not belong to the

reciprocal lattice. For a C lattice the propagation vector k

=(1/2 0 0) is not equivalent to k

=(-1/2 0 0)

because K=2k

-k

=(1 0 0) does not belong to the reciprocal lattice: h+k=2n is the lattice C condition

for components (hkl). On the contrary, the vector (0 0 1/2) is single because (001) is a reciprocal lattice

point of the C lattice.

Microstrains and domain size effects. HKL-dependent shifts and asymmetry

The microstructural effects within FullProf are treated using the Voigt approximation: both instrumental

and sample intrinsic profile are supposed to be described approximately by a convolution of Lorentzian

and Gaussian components. The TCH pseudo-Voigt profile function (Thompson, Cox and Hastings, J.

Appl. Cryst. 20, 79 (1987)) is used to mimic the exact Voigt function and it includes the Finger‘s

treatment of the axial divergence (L.W. Finger, J. Appl. Cryst. 31, 111 (1998)). The integral breadth

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