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beefly在emuch上发布一个帖子 http://emuch.net/html/201105/3149273.html
担心内容,就copy一份过来
ADF的能量分解类似于Morokuma的能量分解。后者应用范围很窄,只适用于闭壳层体系的Hartree-Fock计算,而前者可用于ADF中的各种RDFT和UDFT,甚至还能考虑旋轨耦合。
这个能量分解算例是以前做练习用的,今天偶然从箱底翻出来,既然老有人问类似的问题,就贴在下面。计算需要人工创建分子片,然后组合成HArF分子。本例要分析H-Ar键,所以需要创建的分子片是H和ArF。
#! /bin/sh
$ADFBIN/dirac -n1 <$ADFRESOURCES/Dirac/H
$ADFBIN/dirac -n1 <$ADFRESOURCES/Dirac/Ar
$ADFBIN/dirac -n1 <$ADFRESOURCES/Dirac/F
mv TAPE12 t12.rel
$ADFBIN/adf -n1 < harf.out
Create H file=$ADFRESOURCES/ZORA/TZ2P/H
XC
GGA pbe
End
Relativistic Scalar zora
CorePotentials t12.rel &
H 1
End
End Input
eor
mv TAPE21 H.t21
$ADFBIN/adf -n1 <> harf.out
Create Ar file=$ADFRESOURCES/ZORA/TZ2P/Ar
XC
GGA pbe
End
Relativistic Scalar zora
CorePotentials t12.rel &
Ar 2
End
End Input
eor
mv TAPE21 Ar.t21
$ADFBIN/adf -n1 <> harf.out
Create F file=$ADFRESOURCES/ZORA/TZ2P/F
XC
GGA pbe
End
Relativistic Scalar zora
CorePotentials t12.rel &
F 3
End
End Input
eor
mv TAPE21 F.t21
$ADFBIN/adf <> harf.out
title ArF
atoms
Ar 0.000000 0.000000 0.000000
F 0.000000 0.000000 -1.950000
end
fragments
Ar Ar.t21
F F.t21
end
XC
gga pbe
End
relativistic scalar zora
corepotentials t12.rel &
Ar 2
F 3
end
end input
eor
mv TAPE21 ArF.t21
$ADFBIN/adf << eor >> harf.out
Title test
atoms
H 0.000000 0.000000 1.330000
Ar 0.000000 0.000000 0.000000 f=ArF
F 0.000000 0.000000 -1.950000 f=ArF
end
restricted
CHARGE 0 0
relativistic scalar zora
corepotentials t12.rel &
H 1
Ar 2
F 3
end
integration 6.0
XC
gga pbe
End
fragments
H H.t21
ArF ArF.t21
end
End input
eor
计算完成后,在HArF计算的输出部分找到如下结果:
hartree eV kcal/mol kJ/mol
-------------------- ----------- ---------- -----------
Pauli Repulsion
Kinetic (Delta T^0): 1.782470985375970 48.5035 1118.52 4679.88
Delta V^Pauli Coulomb: -1.136710157595204 -30.9315 -713.30 -2984.43
Delta V^Pauli LDA-XC: -0.183123868092539 -4.9831 -114.91 -480.79
Delta V^Pauli GGA-Exchange: 0.012690279451145 0.3453 7.96 33.32
Delta V^Pauli GGA-Correlation: -0.003832183382116 -0.1043 -2.40 -10.06
-------------------- ----------- ---------- -----------
Total Pauli Repulsion: 0.471495055757255 12.8300 295.87 1237.91
(Total Pauli Repulsion =
Delta E^Pauli in BB paper)
Steric Interaction
Pauli Repulsion (Delta E^Pauli): 0.471495055757255 12.8300 295.87 1237.91
Electrostatic Interaction: -0.117045546884956 -3.1850 -73.45 -307.30
(Electrostatic Interaction =
Delta V_elstat in the BB paper)
-------------------- ----------- ---------- -----------
Total Steric Interaction: 0.354449508872299 9.6451 222.42 930.61
(Total Steric Interaction =
Delta E^0 in the BB paper)
Orbital Interactions
SIGMA: -0.454298601408872 -12.3621 -285.08 -1192.76
PI: -0.006896798127161 -0.1877 -4.33 -18.11
DELTA: 0.000000000000000 0.0000 0.00 0.00
PHI: 0.000000000000000 0.0000 0.00 0.00
-------------------- ----------- ---------- -----------
Total Orbital Interactions: -0.461195399536032 -12.5498 -289.40 -1210.87
Alternative Decomposition Orb.Int.
Kinetic: -1.726978833271678 -46.9935 -1083.70 -4534.18
Coulomb: 1.236130927590834 33.6368 775.68 3245.46
XC: 0.029652506144804 0.8069 18.61 77.85
-------------------- ----------- ---------- -----------
Total Orbital Interactions: -0.461195399536040 -12.5498 -289.40 -1210.87
Residu (E=Steric+OrbInt+Res): -0.000000043854616 0.0000 0.00 0.00
Total Bonding Energy: -0.106745934518349 -2.9047 -66.98 -280.26
Summary of Bonding Energy (energy terms are taken from the energy decomposition above)
======================================================================================
Electrostatic Energy: -0.117045546884956 -3.1850 -73.45 -307.30
Kinetic Energy: 0.055492152104291 1.5100 34.82 145.69
Coulomb (Steric+OrbInt) Energy: 0.099420726141014 2.7054 62.39 261.03
XC Energy: -0.144613265878707 -3.9351 -90.75 -379.68
-------------------- ----------- ---------- -----------
Total Bonding Energy: -0.106745934518357 -2.9047 -66.98 -280.26
H-Ar键的分析过程非常简单,对照这篇文章看就行了(因为手头没有电子版,不清楚具体页码,应该是在比较靠后的位置),需要的数据都在上面列出。由于计算方法不完全一样,所以这个计算的结果可能稍微不同于文献值。
Matthias Lein, Jan Frunzke and Gernot Frenking, Christian Klixbull Jørgensen and the Nature of the Chemical Bond in HArF
http://www.springerlink.com/content/e57dnhpudynhw1yv/
###########################################################################################
文献中的3个能量
然后组合成HArF分子。本例要分析H-----ArF键,
文献键能ΔE是-33.6 kcal/mol beefly的键能是-66.98
#Total Bonding Energy: -0.106745934518357 -2.9047 -66.98 -280.26
文献ΔEpauli=136.5 beefly的键能是295.87
Total Pauli Repulsion: 0.471495055757255 12.8300 295.87 1237.91
文献中ΔEelestat是-62.1 beefly的键能是-73.45
Electrostatic Energy: -0.117045546884956 -3.1850 -73.45 -307.30 这个能量在两行中显示,完全一样,一行是在Steric Interaction下面,另一行是在Summary of Bonding Energy下面
文献中的ΔEorb 是-107.39 beefly的键能是-289.40
Total Orbital Interactions: -0.461195399536032 -12.5498 -289.40 -1210.87
两个人算的
EPA | 文献 | beefly |
ΔEpauli | 136.5 | 295.87 |
ΔEstat | -62.1 | -73.45 |
ΔEorb | -107.39 | -289.40 |
ΔEbond | -33.6 | -66.98 |
能量对比
beefly:由于计算方法不完全一样,所以这个计算的结果可能稍微不同于文献值。
我认为改成差异是较大的,比较合理。
不管怎么说
ΔEbond=ΔEpauli+ΔEstat+ΔEorb 恒成立
以上分析在文殊友大力帮助下完成。
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