大家都用 B3LYP 泛函，可我们对 B3LYP 的历史理解吗？若想了解，请参看：（有时间我

会翻译一下）http://www.ccl.net/chemistry/resources/messages/2002/05/22.008-dir/index.html

大家好，非常感谢大家的回复。尤其感谢 Philip Stephens 教授和 Mike Frisch 博士非常感兴趣

的讲了关于 B3LYP 的故事。我原来的工作要求适当的采用 B3LYP 函数，没有明显的文献指
出是一个明智的选择。所以我现在非常明智的用 DFT，我认为我将来的 B3LYP 会引用到 B3
[1],LYP [2], VWN [3],和它们的组合[4]。根据 Frisch 博士的建议会简单的引用 B3LYP [1,4]。随
时根据自己的需要选择。所有的回复概括如下，消减相关的部分（我最新作出的明智选择），
我也删去了 e-mail 的地址。——Mikael J.
[1] A.D. Becke, J.Chem.Phys. 98 (1993) 5648-5652
[2] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785-789
[3] S.H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 58 (1980) 1200-1211
[4] P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch,
J.Phys.Chem. 98 (1994) 11623-11627
=====================================
Date: Mon, 20 May 2002 18:00:58 +0000
From: philip stephens <stephens_philip -x- at -x- [...]>
To: mikael.johansson -x- at -x- helsinki.fi
题目： B3LYP
感谢你的来信。我的回答如下：早在 1990 我们就对用 DFT 力场预测 VCD 光谱很感兴
趣（自从我们知道 HF 力场不够精确，MP2 力场会给出好一点的结果但计算太昂贵）。一些
不成功 DFT 尝试后，我们开始和 Mike Frisch 合作高斯，分析二阶导数开始生效。Mike
Thank you for your email. I can answer you as follows: in the early
1990s we (at USC) were interested in using DFT harmonic force fields in
predicting VCD spectra ( since we already knew that HF force fields were of
insufficient accuracy and that MP2 force fields gave much better results,
but were computationally too expensive). After some unsuccessful initial
attempts with numerical DFT force fields, we began a collaboration with Mike
Frisch at Gaussian at the time that analytical second derivatives had just
been implemented. Mike was interested in using the comparison of predicted
vibrational spectra to experiment as a way of evaluating the relative
accuracies of different functionals. We therefore studied a number of
molecules using a range of functionals. The hybrid functionals of Becke had
just been introduced and were of particular interest. For reasons that are
unknown to me Mike decided to create a new hybrid functional - the now
famous B3LYP - and this was included as well as the Becke functional -
B3PW91. It turned out to be a good idea!
So, the short answer to your question is: the B3LYP functional used in our
work and used in the Gaussian program was invented by Mike Frisch. If you
want more of the history of this situation you should contact Mike directly:
frisch -x- at -x- [...].
By the way, there is another paper with the definition of B3LYP spelled
out and some further discussion of its composition: Stephens, Devlin,
Ashvar, Chabalowski and Frisch, Disc. Faraday Soc. vol 99, pp103-119, 1994.
[...]
===========================================
Date: Tue, 21 May 2002 13:39:55 -0400 (EDT)
From: Mike Frisch <frisch -x- at -x- [...]>
To: uunet!helsinki.fi!mikael.johansson -x- at -x- uunet.uu.net
Subject: Re: Origins of B3LYP
[...]
When I first decided to make use of Becke's parametrization based on
adiabatic connection, we had not yet coded the PW91 correlation functional
in Gaussian. We had coded the earlier Perdew correlation functional (P86)
but found that LYP seemed to work better for molecules. I felt that if the
parameters Becke had optimized represented real physical content in the
model and not just curve fitting, then the same values should be useful with
other functionals of the same general type (i.e., GGAs). So I tested the
same parameters with BLYP instead of BPW91, and found that indeed they gave a
similar improvement in predicted energetics. Just as importantly, the
parameters, which Becke fit to dissociation energies of neutral molecules at
fixed geometries, also improved predicted structures and vibrational
frequencies as compared to pure DFT, and also worked well for ionization
potentials and electron affinities. So both the transferability of the
parameters to different functionals and the fact that parameters fit to one
property improve virtually all other properties confirmed that Becke's scheme
improves the physical content of the model and is not just fitting a
particular type of property.
The reason for including VWN was that, unlike most correlation functionals,
LYP does not have distinct local and gradient-corrected terms. So to adjust
the amount of non-local correlation from LYP as required by Becke's
parameters, I needed to use a separate local correlation functional.
That is, instead of Becke's:
1.0 x (local correlation) + 0.81 XC(gradient-correction for correlation)
I did
0.81 (LYP local+gradient-correction) + 0.19 (VWN3 local)
Unfortunetly, I wasn't as precise as I should have been in the paper and
didn't specify which version of VWN (VWN3) I used for the local
correlation. This has led to a bit of confusion, with some people using
VWN5 in their implementations for the local part. The difference between
the two versions is a small variation in total energy, but the predictions
are basically the same regardless of which local functional is used to
provide the small non-gradient-corrected part.
We have since coded PW91 and found that B3PW91 is not quite as good as
B3LYP. I think this reflects the fact that PW91 isn't as good as LYP for
molecules, not any difference in optimal values for the 3 parameters. PW91
is exact for the uniform electron gas, which physicist like, while LYP is
wrong in this limit. However, LYP was designed to make He come out right.
Since He is a better example of the highly non-uniform electron density
in molecules than the uniform electron gas, it is not surprising that BLYP
and B3LYP are (slightly) better approximations for molecules than BPW91 and
B3PW91.
===========================================
Date: Wed, 15 May 2002 13:58:55 -0400 (EDT)
From: Dmitry Khoroshun <dima -x- at -x- [...]>
To: Mikael Johansson <mpjohans -x- at -x- pcu.helsinki.fi>
Subject: Re: CCL:Proper B3LYP reference?
你好，你可能想引用下面的文献 Hertwig, R. H.; Koch, W. Chem. Phys. Lett. 1997, 268,
345
Becke-3-LYP 是不是局部对比函数参数化
=====================================
Date: Wed, 15 May 2002 14:12:46 -0400
From: James Kubicki <kubicki -x- at -x- geosc.psu.edu>
To: mpjohans -x- at -x- pcu.helsinki.fi
Subject: Re: CCL:合适的引用 B3LYP
你可以尝试 Becke A. D., Density-functional exchange-energy approximation with
correct asymptotic-behavior. Phys. Rev. A, 38(6), 3098, 1988.
[...]
=====================================
Date: Wed, 15 May 2002 14:57:10 -0400
From: elewars <elewars -x- at -x- [...]>
To: Mikael Johansson <mpjohans -x- at -x- pcu.helsinki.fi>
Subject: Re: CCL:Proper B3LYP reference?
Re the question below about citing B3LYP
The B3LYP functional is based on an exchange-correlation functional
developed by Becke in 1993 and modified by stevens in 1994 by introduction
of the Lee-Yang-Parr 1988 correlation functional. I would cite B3LYP as:
P. J. Stephens, F. J. Devlin, C. F. Chablowski, and M. Frisch, J. Phys.
Chem. 1994, 98, 11623, and refs therein.
E. Lewars
=====================================
Date: Thu, 16 May 2002 09:11:25 +0200
From: Patrik Johansson <patrikj -x- at -x- [...]>
To: Mikael Johansson <mpjohans -x- at -x- pcu.helsinki.fi>
Subject: Re: CCL:Proper B3LYP reference?
Hej Mikael
Jag har alltid anvant [1] tillsammans med orginal "LYP":
Lee, Yang, Parr: Phys Rev B, 1988, 37, 785.
Och om jag inte missminner mig tror jag mig ha last att detta ar de som
ska anvandas som referenser (minimum alltsa). Detta aven om inte den
"LYP" ar exakt den som anvands i B3LYP.
[...]
===========================================
Date: Thu, 16 May 2002 09:23:02 -0400 (EDT)
From: Doug Fox <gaussian.com!fox -x- at -x- [...]>
To: Mikael Johansson
<uunet!pcu.helsinki.fi!mpjohans%[...] -x- at -x- uunet.uu.net>
Subject: Re: CCL:Proper B3LYP reference?
The combination of [2] and [1] is the recommended reference. The
combination was developed by Gaussian and then reported in applications
papers. Becke's paper documents the theory behind the coefficients
of this hybrid method.
[...]
============================================
Date: Thu, 16 May 2002 10:55:43 +0300 (EEST)
From: Michael Patzschke <michaelp -x- at -x- [...]>
To: Mikael Johansson <mpjohans -x- at -x- chem.helsinki.fi>
Subject: B3LYP
[...]
B3LYP historien &auml;r faktiskt lite sv&aring;rt att f&ouml;lja med. Men om jag
har
f&ouml;rst&aring;tt det r&auml;tt. s&aring; b&ouml;rjade det hela med utvecklingen
av hybridmethoder
s&aring; som HH (Becke 92) vilka anv&auml;nder 'adiabatic connection' (Becke 88).
HH
methoden var inte s&aring; v&auml;rst framg&aring;ngsrik och Becke kom sen med ett
f&ouml;reslag
som baserade p&aring; CGA (och inte p&aring; LDA som Beckes HH method) den blev
k&auml;nd
som B3 (Becke 93). Allt detta betr&auml;ffa dock bara 'exchange' delen. I Becke
93 anv&auml;ndes B3 tillsammans med PW91 'correlation' funktionalen (Perdew
92). F&ouml;rst senare (Stephens 94) kom f&ouml;reslaget att anv&auml;nda B3 och
LYP
funktionalen (Lee 88). Och fortfarande finns det oklarheter vilken av
Beckes B3-formler borde anv&auml;ndas (se t.ex. Hertwig 97). &Auml;nnu
v&auml;rre, s&aring;
finns det m&aring;nga olika sett att skriva LYP-funktionalen (se Miehlich 89
och Lee 93).
[...]
Becke 88 J.Chem.Phys.,1988,88,1053
Lee 88 Phys.Rev.,1988,B37,785
Miehlich 89 Chem.Phys.Lett.,1989,157,200
Becke 92 J.Chem.Phys.,1992,98,1372
Perdew 92 Phys.Rev.,1992,B46,6671
Becke 93 J.Chem.Phys.,1993,98,5648
Lee 93 Phys.Rev.B,1993,37,785
Stephens 94 J.Phys.Chem.,1994,98,11623
Hertwig 97 Chem.Phys.Lett.,1997,268,345
===============================================
Date: Wed, 15 May 2002 20:08:30 +0300 (EET DST)
From: Mikael Johansson <mpjohans -x- at -x- pcu.helsinki.fi>
To: <chemistry -x- at -x- ccl.net>
Subject: Proper B3LYP reference?
Hello All!
What's the "proper" B3LYP reference to use? Usually Becke's paper [1]
is
cited, and sometimes additionally the paper by Stephens et al. [2].
Paper [1] does not contain the B3LYP-functional, altough it defines the 3
parameters for the different types of contribution. Paper [2] explicitly
explains the alterations to Becke's original formulation, but I find
at least one earlier paper [3] mentioning/using B3LYP.
> From the articles, I assume B3LYP was something introduced by the Gaussian
program package, am I right? Furthermore, does anyone know of an even
earlier B3LYP reference than [3]?
[1] A.D. Becke, J.Chem.Phys. 98 (1993) 5648-5652
[2] P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J Frisch,
J.Phys.Chem. 98 (1994) 11623-11627
[3] K. Kim, K.D. Jordan, J.Phys.Chem. 98 (1994) 10089-10094
Have a nice day,

总结一下：
１。xc －LYP （1988）
２。c－VWN （1980）
３。Becke's:发明杂化泛函(1993)
1.0 x (local correlation) + 0.81 XC(gradient-correction for correlation)
４。Frisch：发明 B ３ LYP（高斯里面用的, 1994）
0.81 (LYP local+gradient-correction) + 0.19 (VWN3 local)
＂The reason for including VWN was that, unlike most correlation functionals, LYP does not have
distinct local and gradient-corrected terms. ＂

对于我的震惊程度犹如知道 Kon－Sham 的 Sham 是沈呂九一样

1# lihb734
总结一下：
１。xc －LYP （1988）
２。c－VWN （1980）
３。Becke's:发明杂化泛函(1993)
1.0 x (local correlation) + 0.81 XC(gradient-correction for
correlation)
４。Frisch：发明 B ３ LY ...
chao 发表于 2009-11-20 04:36
对于我来说，也是同样如此啊。