- 功函数是指导体的费米能级到真空能级的差值
- 电离势（ionic potential）是指价带顶（VBM）能级到真空能级的差值
- 亲和能（electron affinity）是指导带底(CBM)能级到真空能级的差值
在DFT计算中，真空能级需要建立slab平板模型引入足够厚度的真空层来计算。
晶胞CELL中留空的区域即是真空，电荷密度基本为0，所以势能是常数，即真空能级。
但是在slab计算中，由于表面态的存在，费米能级不准确；而slab内的平均势能和真空平均势能是准确的。
在bulk计算中，费米能级和平均势能的差值是准确的。
认为slab内平均势能和bulk平均势能是对应的（可用于标定），则可以得到真空能级和费米能级的差值，即功函数。相关文献：
https://journals.aps.org/prb/abstract/10.1103/PhysRevB.69.035320
建立slab模型
- 为了获取真空能级，需要向体系引入足够厚的真空层（不小于15Å）。
- 为了让slab模型的内部静电势和bulk模型一致，需要在添加真空层的方向将体系扩胞，以创造脱离了表面态影响的内部区域。
VESTA
导入 cif 文件
Edit - Edit Data - Unit Cell - Transform 进行扩胞
选择“是”
选择前两个选项都可以
Edit - Edit Data - Unit Cell - Transform 将体系整体沿着 Z 轴（加真空方向）平移，让所有原子都位于当前原胞。
获得 1*1*2 super cell
File - Export Data 导出数据为 POSCAR ，坐标为直接坐标
打开刚刚导出的POSCAR文件，修改要添加真空层的方向的晶格矢量（添加真空层）
保存退出，导入VESTA。发现真空层已经被加入
Material Studio
将结构导入MS
选择 Build - Surfaces - Cleave Surface 打开切面界面
选择切面 Miller 指数，MS会从设置的 Top 位置(top boundary)，向下切 Thickness 厚度，作为 slab单胞用于周期重复。
因此切面时，通过Top控制暴露面，通过Thickness控制slab厚度/层数。
选择 Build → Crystals → Build Vacuum Slab 打开添加真空层界面，选择合适的真空层厚度(Vacuum thickness)，点击Build后slab模型建立完毕
后续如果想要在slab面内扩胞，也是通过 Build - Symmetry - Super cell 进行扩胞即可。
slab模型静电势计算
结构优化
一般采用固定中间数层原子，仅允许靠近表面的原子进行弛豫。以此来模拟暴露于真空的表面态。
&CONTROL
calculation = 'relax'
restart_mode = 'from_scratch'
outdir = './tmp'
pseudo_dir = '~/SSSP'
prefix = 'MAPbBr3-H'
verbosity = 'low'
etot_conv_thr = 1.D-4
forc_conv_thr = 1.D-4
nstep = 200
/
&SYSTEM
ibrav = 0
nat = 69
ntyp = 5
ecutwfc = 44.0
ecutrho = 300.0
occupations = 'smearing'
degauss = 0.005
smearing = 'gaussian'
/
&ELECTRONS
electron_maxstep = 128
conv_thr = 1.D-6
mixing_mode = 'plain'
mixing_beta = 0.7
mixing_ndim = 8
diagonalization = 'david'
/
&IONS
ion_dynamics = 'bfgs'
/
CELL_PARAMETERS angstrom
5.932817000 0.000000000 0.000000000
0.000000000 5.932817000 0.000000000
0.000000000 0.000000000 75.091716000
ATOMIC_SPECIES
Br 79.904 Br.UPF
C 12.011 C.UPF
H 1.008 H.UPF
N 14.007 N.UPF
Pb 207.2 Pb.UPF
ATOMIC_POSITIONS angstrom
N 0.338229000 0.002196000 27.711300000
H 1.370294000 0.003678000 27.660497000
H 0.068264000 0.842077000 28.258501000
H 0.070818000 5.094982000 28.259596000
H 0.107324000 5.036413000 31.865829000 0 0 0
H 0.081813000 0.900718000 31.867332000 0 0 0
H 4.593589000 5.913459000 32.456048000 0 0 0
Br 2.592693000 2.976782000 32.822495000 0 0 0
Br 5.868844000 2.969366000 29.582296000 0 0 0
Br 3.159394000 0.006111000 29.618340000 0 0 0
C 5.683444000 5.929596000 32.385462000 0 0 0
Pb 2.926888000 2.971502000 29.929971000 0 0 0
N 0.313964000 0.002314000 33.761138000 0 0 0
H 1.347042000 0.009433000 33.774655000 0 0 0
H 0.010145000 0.839373000 34.292786000 0 0 0
H 0.021833000 5.093902000 34.292786000 0 0 0
H 0.107324000 5.036413000 37.798057000 0 0 0
H 0.081813000 0.900718000 37.800310000 0 0 0
H 4.593589000 5.913459000 38.388277000 0 0 0
Br 2.592693000 2.976782000 38.754723000 0 0 0
Br 5.868844000 2.969366000 35.515276000 0 0 0
Br 3.159394000 0.006111000 35.551320000 0 0 0
C 5.683444000 5.929596000 38.317691000 0 0 0
Pb 2.926888000 2.971502000 35.862949000 0 0 0
N 0.313964000 0.002314000 39.694119000 0 0 0
H 1.347042000 0.009433000 39.707634000 0 0 0
H 0.010145000 0.839373000 40.225766000 0 0 0
H 0.021833000 5.093902000 40.225766000 0 0 0
H 5.925412000 5.032171000 43.795718000
H 5.922118000 0.897827000 43.789000000
H 4.498407000 5.932093000 44.405492000
Br 2.624417000 2.914598000 44.909188000
Br 5.868844000 2.969366000 41.448255000 0 0 0
Br 3.159394000 0.006111000 41.484299000 0 0 0
C 5.587983000 5.932748000 44.317894000
Pb 2.926888000 2.971502000 41.795178000 0 0 0
N 0.247314000 0.007123000 45.688754000
H 1.279332000 0.023242000 45.668449000
H 5.890055000 0.845171000 46.228664000
H 5.911421000 5.095027000 46.229466000
H 0.356815000 5.033727000 19.836386000
H 5.152297000 5.029181000 50.833801000
H 0.355112000 0.900093000 19.837200000
H 5.140295000 0.891776000 50.731842000
H 4.751018000 5.931697000 20.096436000
H 5.655169000 0.078982000 52.242609000
Br 2.662311000 2.968907000 20.838543000
Br 2.649578000 2.967950000 51.043990000
Br 5.813232000 2.974481000 47.659246000
Br 2.941016000 5.924479000 47.817583000
C 5.832607000 5.932693000 20.262010000
C 5.652159000 0.018041000 51.149580000
Pb 2.869747000 2.958803000 47.899165000
N 0.157916000 5.932168000 21.728328000
N 1.128902000 0.001607000 50.670799000
H 1.173381000 5.932588000 21.952747000
H 1.203248000 5.913635000 49.637924000
H 5.695801000 0.839708000 22.192304000
H 1.644853000 0.869282000 50.958095000
H 5.696761000 5.090826000 22.191492000
H 1.642431000 5.077978000 50.992354000
H 0.008527000 5.033202000 25.830159000
H 0.005761000 0.899663000 25.828497000
H 4.542698000 5.931235000 26.503735000
Br 2.678932000 2.971550000 26.931939000
Br 5.728778000 2.966264000 23.550955000
Br 2.925161000 0.001063000 23.678521000
C 5.627335000 0.000047000 26.367513000
Pb 2.778007000 2.967511000 23.687878000
K_POINTS automatic
4 4 1 0 0 0在QE中，固定原子的方法为在相应的原子坐标后添加 0 0 0 （三个0分别代表固定xyz方向坐标）
像这里，我选择固定了中间的三层原子，允许靠近表面两侧的一层原子移动
结构优化完得到
发现最右侧的MA阳离子由于缺少周期性的无机八面体的约束，被上一个周期的八面体拉动转向。
自洽计算
正常进行自洽计算
&CONTROL
calculation = 'scf',
prefix = 'MAPbBr3-slab',
pseudo_dir = '~/SSSP',
outdir = './tmp',
/
&SYSTEM
ibrav = 0
nat = 69
ntyp = 5
ecutwfc = 50.0
ecutrho = 500.0
occupations = 'smearing'
degauss = 0.2
smearing = 'gaussian'
/
&ELECTRONS
conv_thr = 1.0d-8,
mixing_beta = 0.2,
/
ATOMIC_SPECIES
H 1.00794 H.UPF
Pb 207.2 Pb.UPF
C 12.0107 C.UPF
Br 79.904 Br.UPF
N 14.00674 N.UPF
CELL_PARAMETERS angstrom
5.932817000 0.000000000 0.000000000
0.000000000 5.932817000 0.000000000
0.000000000 0.000000000 75.091716000
ATOMIC_POSITIONS (angstrom)
N 0.3481084606 0.0023004978 27.7117231058
H 1.3794787374 0.0030295034 27.6510897300
H 0.0841089470 0.8425341968 28.2613859615
H 0.0854925602 5.0948334463 28.2620589011
H 0.1073240000 5.0364130000 31.8658290000 0 0 0
H 0.0818130000 0.9007180000 31.8673320000 0 0 0
H 4.5935890000 5.9134590000 32.4560480000 0 0 0
Br 2.5926930000 2.9767820000 32.8224950000 0 0 0
Br 5.8688440000 2.9693660000 29.5822960000 0 0 0
Br 3.1593940000 0.0061110000 29.6183400000 0 0 0
C 5.6834440000 5.9295960000 32.3854620000 0 0 0
Pb 2.9268880000 2.9715020000 29.9299710000 0 0 0
N 0.3139640000 0.0023140000 33.7611380000 0 0 0
H 1.3470420000 0.0094330000 33.7746550000 0 0 0
H 0.0101450000 0.8393730000 34.2927860000 0 0 0
H 0.0218330000 5.0939020000 34.2927860000 0 0 0
H 0.1073240000 5.0364130000 37.7980570000 0 0 0
H 0.0818130000 0.9007180000 37.8003100000 0 0 0
H 4.5935890000 5.9134590000 38.3882770000 0 0 0
Br 2.5926930000 2.9767820000 38.7547230000 0 0 0
Br 5.8688440000 2.9693660000 35.5152760000 0 0 0
Br 3.1593940000 0.0061110000 35.5513200000 0 0 0
C 5.6834440000 5.9295960000 38.3176910000 0 0 0
Pb 2.9268880000 2.9715020000 35.8629490000 0 0 0
N 0.3139640000 0.0023140000 39.6941190000 0 0 0
H 1.3470420000 0.0094330000 39.7076340000 0 0 0
H 0.0101450000 0.8393730000 40.2257660000 0 0 0
H 0.0218330000 5.0939020000 40.2257660000 0 0 0
H 5.9824697200 5.0375083905 43.8734645553
H 5.9672295449 0.9033428315 43.8655710130
H 4.5551332578 5.9277356977 44.4950111529
Br 2.6918040785 2.9553124195 44.9403344561
Br 5.8688440000 2.9693660000 41.4482550000 0 0 0
Br 3.1593940000 0.0061110000 41.4842990000 0 0 0
C 5.6438358034 5.9363463813 44.3976231530
Pb 2.9268880000 2.9715020000 41.7951780000 0 0 0
N 0.3149583624 0.0146588936 45.7632109167
H 1.3467784843 0.0284435170 45.7331236748
H 5.9630884893 0.8546195499 46.3036215742
H 5.9829708482 5.1037075280 46.3080487733
H 0.3695047505 5.0341030495 19.8368559770
H 5.1640359130 5.0357547878 50.8345736204
H 0.3670151508 0.9007058014 19.8371552921
H 5.1627269585 0.9006938211 50.8362619210
H 4.7623452497 5.9316017132 20.0899407511
H 5.6857636156 0.0006153194 52.2925773806
Br 2.6644388192 2.9695123501 20.8380136384
Br 2.6799009703 2.9688506946 51.0750637341
Br 5.8767562693 2.9796808947 47.7224840089
Br 3.0164337139 5.9372712818 47.8770215110
C 5.8431045094 5.9331157199 20.2602063485
C 5.6729553227 0.0018120618 51.1980956150
Pb 2.9253239462 2.9709544065 47.9324492797
N 0.1613128634 5.9331379849 21.7277790713
N 1.1454915069 0.0028675701 50.7064704163
H 1.1757051682 5.9341562336 21.9569513009
H 1.2104991195 5.9356044632 49.6733723877
H 5.6970481592 0.8407716619 22.1897692552
H 1.6628656178 0.8650482349 51.0071061496
H 5.6988883775 5.0915958709 22.1894468185
H 1.6635470948 5.0741203793 51.0075599085
H 0.0066778006 5.0344887783 25.8333297692
H 0.0037182236 0.9010902430 25.8328674476
H 4.5439593534 5.9319775056 26.5140231666
Br 2.6790872955 2.9723037761 26.9281608533
Br 5.7274292480 2.9673582058 23.5526716963
Br 2.9208102493 0.0022573405 23.6872948717
C 5.6279150670 0.0010073249 26.3724957549
Pb 2.7765060695 2.9687099714 23.6880467963
K_POINTS {automatic}
6 6 1 0 0 0
加偶极修正的自洽计算
(添加参数
$CONTROL
...
tefield = .true. !开启电场
dipfield = .true. !开启偶极修正功能
/
&SYSTEM
...
edir = 3 !添加电场的方向
eamp = 0 !自动计算修正电场（偶极矩）大小
emaxpos = 0.99 !外加偶极矩的起始位置
eopreg = 0.01 !外加偶极矩的衰减宽度
/
)
这里要注意，添加偶极修正时，原子位置不能与外加偶极矩区域重合，否则会导致无法收敛。
&CONTROL
calculation = 'scf',
prefix = 'MAPbBr3-slab',
pseudo_dir = '~/SSSP',
outdir = './tmp',
tefield = .true.
dipfield = .true.
/
&SYSTEM
ibrav = 0
nat = 69
ntyp = 5
ecutwfc = 50.0
ecutrho = 500.0
occupations = 'smearing'
degauss = 0.2
smearing = 'gaussian'
edir = 3
eamp = 0
/
&ELECTRONS
conv_thr = 1.0d-8,
mixing_beta = 0.2,
/
ATOMIC_SPECIES
H 1.00794 H.UPF
Pb 207.2 Pb.UPF
C 12.0107 C.UPF
Br 79.904 Br.UPF
N 14.00674 N.UPF
CELL_PARAMETERS angstrom
5.932817000 0.000000000 0.000000000
0.000000000 5.932817000 0.000000000
0.000000000 0.000000000 75.091716000
ATOMIC_POSITIONS (angstrom)
N 0.3481084606 0.0023004978 27.7117231058
H 1.3794787374 0.0030295034 27.6510897300
H 0.0841089470 0.8425341968 28.2613859615
H 0.0854925602 5.0948334463 28.2620589011
H 0.1073240000 5.0364130000 31.8658290000 0 0 0
H 0.0818130000 0.9007180000 31.8673320000 0 0 0
H 4.5935890000 5.9134590000 32.4560480000 0 0 0
Br 2.5926930000 2.9767820000 32.8224950000 0 0 0
Br 5.8688440000 2.9693660000 29.5822960000 0 0 0
Br 3.1593940000 0.0061110000 29.6183400000 0 0 0
C 5.6834440000 5.9295960000 32.3854620000 0 0 0
Pb 2.9268880000 2.9715020000 29.9299710000 0 0 0
N 0.3139640000 0.0023140000 33.7611380000 0 0 0
H 1.3470420000 0.0094330000 33.7746550000 0 0 0
H 0.0101450000 0.8393730000 34.2927860000 0 0 0
H 0.0218330000 5.0939020000 34.2927860000 0 0 0
H 0.1073240000 5.0364130000 37.7980570000 0 0 0
H 0.0818130000 0.9007180000 37.8003100000 0 0 0
H 4.5935890000 5.9134590000 38.3882770000 0 0 0
Br 2.5926930000 2.9767820000 38.7547230000 0 0 0
Br 5.8688440000 2.9693660000 35.5152760000 0 0 0
Br 3.1593940000 0.0061110000 35.5513200000 0 0 0
C 5.6834440000 5.9295960000 38.3176910000 0 0 0
Pb 2.9268880000 2.9715020000 35.8629490000 0 0 0
N 0.3139640000 0.0023140000 39.6941190000 0 0 0
H 1.3470420000 0.0094330000 39.7076340000 0 0 0
H 0.0101450000 0.8393730000 40.2257660000 0 0 0
H 0.0218330000 5.0939020000 40.2257660000 0 0 0
H 5.9824697200 5.0375083905 43.8734645553
H 5.9672295449 0.9033428315 43.8655710130
H 4.5551332578 5.9277356977 44.4950111529
Br 2.6918040785 2.9553124195 44.9403344561
Br 5.8688440000 2.9693660000 41.4482550000 0 0 0
Br 3.1593940000 0.0061110000 41.4842990000 0 0 0
C 5.6438358034 5.9363463813 44.3976231530
Pb 2.9268880000 2.9715020000 41.7951780000 0 0 0
N 0.3149583624 0.0146588936 45.7632109167
H 1.3467784843 0.0284435170 45.7331236748
H 5.9630884893 0.8546195499 46.3036215742
H 5.9829708482 5.1037075280 46.3080487733
H 0.3695047505 5.0341030495 19.8368559770
H 5.1640359130 5.0357547878 50.8345736204
H 0.3670151508 0.9007058014 19.8371552921
H 5.1627269585 0.9006938211 50.8362619210
H 4.7623452497 5.9316017132 20.0899407511
H 5.6857636156 0.0006153194 52.2925773806
Br 2.6644388192 2.9695123501 20.8380136384
Br 2.6799009703 2.9688506946 51.0750637341
Br 5.8767562693 2.9796808947 47.7224840089
Br 3.0164337139 5.9372712818 47.8770215110
C 5.8431045094 5.9331157199 20.2602063485
C 5.6729553227 0.0018120618 51.1980956150
Pb 2.9253239462 2.9709544065 47.9324492797
N 0.1613128634 5.9331379849 21.7277790713
N 1.1454915069 0.0028675701 50.7064704163
H 1.1757051682 5.9341562336 21.9569513009
H 1.2104991195 5.9356044632 49.6733723877
H 5.6970481592 0.8407716619 22.1897692552
H 1.6628656178 0.8650482349 51.0071061496
H 5.6988883775 5.0915958709 22.1894468185
H 1.6635470948 5.0741203793 51.0075599085
H 0.0066778006 5.0344887783 25.8333297692
H 0.0037182236 0.9010902430 25.8328674476
H 4.5439593534 5.9319775056 26.5140231666
Br 2.6790872955 2.9723037761 26.9281608533
Br 5.7274292480 2.9673582058 23.5526716963
Br 2.9208102493 0.0022573405 23.6872948717
C 5.6279150670 0.0010073249 26.3724957549
Pb 2.7765060695 2.9687099714 23.6880467963
K_POINTS {automatic}
6 6 1 0 0 0
静电势计算
利用 pp.x 计算静电势
pp.x < pp.in > pp.out
输入文件 pp.in 内容如下
&inputpp
prefix = 'MAPbBr3-slab', ! 项目名称
outdir = './tmp/', ! 临时目录，需与之前计算的一致
filplot = 'pp11.dat', ! 输出电势文件
plot_num = 11, ! 选择11, 计算静电势
/然后利用后处理程序 average.x 在真空方向取平均
average.x < aver.in > aver.out
输入文件 aver.in 内容如下
（参数说明：https://github.com/QEF/q-e/blob/master/PP/src/average.f90）
1 ！读取文件个数，nfile
pp11.dat !读取静电势的文件，filename
1 ！上一个文件的权重，weight
3000 ！ 插值点数，npt
3 ！ 移动平均计算方向，idir
11 ！宏观窗口大小（a.u.），awin计算完成会产生一个 .dat 数据文件
共三列，
第一列为沿加真空层方向坐标
第二列为静电势在xy平面平均值
第三列为静电势xy平面平均值在z方向移动平均大小
绘图如下：
bulk模型的静电势计算
除了使用的 cif 模型与slab不同，其他地方均与slab模型中的计算流程一致。即
结构优化（pw.x-relax） ---- 自洽计算（pw.x-scf） ---- 静电势计算（pp.x-11） ---- 取平均（average.x）
算出的结果为（纵坐标单位为Ry）
slab内部静电势对准
将slab模型和bulk模型计算得到的静电势曲线绘制于同一张图内
因为在晶体内部，静电势应该是一样的（slab内部足够深处的静电势环境应该与bulk一致）
所以可以利用这一点进行对准
对准后，两个体系的能量相当于拥有同一个参考平面，就可以将slab模型计算的真空能级能量与bulk模型计算的费米能级能量作差，获得功函数
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