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标题: 科学杂志发表了一篇DFT泛函的文献，大牛公开撕了 [打印本页]

作者
Author: jiangning198511 时间: 2017-1-8 12:25
标题: 科学杂志发表了一篇DFT泛函的文献，大牛公开撕了
本帖最后由 jiangning198511 于 2017-1-16 08:54 编辑

如何构造泛函在DFT中非常重要，目前主要有原理派和拟合派，Perdew 和Truhlar 分别是代表人物。最近 Perdew等人在自然杂志上发表文章，题目就是密度泛函已经偏离了通向精确泛函的大道，直接打脸拟合派。不知道T大牛如何反击。

Density functional theory is straying from the path toward the exact functional ！！
(, 下载次数 Times of downloads: 461)

管理员Sobereva注：此文的补充材料见此 (, 下载次数 Times of downloads: 102)

作者
Author: 我本是个娃娃 时间: 2017-1-8 12:30
新派剑宗和气宗

作者
Author: 遗忘爱神 时间: 2017-1-8 13:47
可是这不是Science吗

作者
Author: wswrpd 时间: 2017-1-8 14:11
吃瓜群众表示我不懂，那个好用用哪个

作者
Author: greatzdk 时间: 2017-1-8 14:20
加把火
http://arstechnica.com/science/2 ... y-be-getting-worse/

作者
Author: helpme 时间: 2017-1-8 17:03

我本是个娃娃发表于 2017-1-8 12:30
新派剑宗和气宗

真的就是这个意思。后面应该还有后续，期待。

作者
Author: Mirror 时间: 2017-1-9 08:49
真理越辩越明，希望争论出有意义的结果

作者
Author: asdf 时间: 2017-1-9 15:20
引用了Multiwfn：
Conversion of wfn files into RDF tables (50000 radial points, range: 0-10 Å) was
done by Multiwfn (29)......All descriptors are used as implemented in Multiwfn......

作者
Author: chrinide 时间: 2017-1-9 15:55
实用主义和真理派之争（M系列只关注能量导致density错得越来越远，也就离精确泛函越来越远了）

说实话我从不用 M系的泛函

作者
Author: sobereva 时间: 2017-1-10 00:13

asdf 发表于 2017-1-9 15:20
引用了Multiwfn：
Conversion of wfn files into RDF tables (50000 radial points, range: 0-10 Å) ...

哎呦，此文前几天由于太忙就只扫了一眼，我都没注意。
脸上有光

记得以前有人通过邮件问过我计算径向密度的事，没想最后搞了篇science
现在几个理论大腕perdew、truhlar、grimme都有文章引过Multiwfn了

作者
Author: 遗忘爱神 时间: 2017-1-10 11:32

sobereva 发表于 2017-1-10 00:13
哎呦，此文前几天由于太忙就只扫了一眼，我都没注意。
脸上有光
记得以前有人通过邮件问过我计 ...

multiwfn确实被各路大牛推荐过

作者
Author: brothers 时间: 2017-1-10 17:03

sobereva 发表于 2017-1-10 00:13
哎呦，此文前几天由于太忙就只扫了一眼，我都没注意。
脸上有光
记得以前有人通过邮件问过我计 ...

绝对要赞~！

作者
Author: ORCA_in_TCC 时间: 2017-1-11 13:38

sobereva 发表于 2017-1-10 00:13
哎呦，此文前几天由于太忙就只扫了一眼，我都没注意。
脸上有光
记得以前有人通过邮件问过我计 ...

作者
Author: Mikasa 时间: 2017-1-11 16:40
另外一篇Perspective
A conundrum for density functional theory：DFT studies may sometimes get the right results for the wrong reasons

作者
Author: 物理小笨 时间: 2017-1-12 16:13

sobereva 发表于 2017-1-10 00:13
哎呦，此文前几天由于太忙就只扫了一眼，我都没注意。
脸上有光
记得以前有人通过邮件问过我计 ...

👍

作者
Author: stecue 时间: 2017-1-13 02:41

sobereva 发表于 2017-1-10 00:13
哎呦，此文前几天由于太忙就只扫了一眼，我都没注意。
脸上有光
记得以前有人通过邮件问过我计 ...

大赞啊，已经成标准工具了。

作者
Author: plus 时间: 2017-1-13 10:58
用极端的体系测试肯定会超出拟合参数用的体系的范围，使结果偏差更大。

作者
Author: yflchx 时间: 2017-1-13 17:40
好像没有测试双杂化泛函，不知道效果怎么样？

作者
Author: coolrainbow 时间: 2017-1-13 22:35
反了吧？Truhlar才是拟合派

作者
Author: laomalao 时间: 2017-1-14 05:49
m系列的基本中枪我了个去

作者
Author: jiangning198511 时间: 2017-1-16 08:54

coolrainbow 发表于 2017-1-13 22:35
反了吧？Truhlar才是拟合派

笔误已经修改

作者
Author: xiesilent 时间: 2017-1-24 13:56
U of Minnesota people and more others agree that this anti-Minnesota Functional paper is ridiculous, silly and insane! 可能叫这个名字更合适 "Oh goody! We finally found a criterion by which Truhlar's functionals come out worst." 一个DFT functional本来就不可能在各方面都作到准确，选择像Ne8+, F7+这样的高电荷非典型双电子结构本来就不合理。
Hammes-Shiffer在她的comment中也表现出不推崇这篇文章。

作者
Author: tigerhoffman 时间: 2017-1-24 15:41
高手过招，华山论道，厉害

作者
Author: sobereva 时间: 2017-1-27 17:40
搬运一下CCL上某人对此文章的看法，有一定道理。即便只是讨论密度的准确性，测试体系的局限性也太大

A recent issue of Science contained an interesting article "Density functional theory is
straying from the path toward the exact functional"[1].

I agree with the article's main idea that new DFT functional development should focus on both reproducing the energies and the electron densities. I also agree with the article's statement that one should be cautious to make sure new functionals obey appropriate limits and norms without using an excessive number of empirically fitted parameters.

However, there is a notable limitation in their methodology. Specifically, in the article they claim that "The results for molecules would be ambiguous because for typical approximate functionals, accurate molecular energies and densities arise only from an understood but uncontrollable error cancellation between a functional’s exchange and correlation components" I do not agree with this, because many energetic properties of molecules have been measured unambiguously using spectroscopic techniques. Also, it is possible to unambiguously compute the energy and geometry that is theoretically predicted by each functional for a chosen molecule. So, it is in fact possible to unambiguously compare theoretically computed and experimentally measured energies for molecules. Moreover, the authors used CCSD calculations as the reference data for the electron densities of single atoms, and the CCSD method can be applied to molecules not just single atoms.

The authors reported the electron density errors for isolated closed-shell atoms and atomic cations only, while citing the energy errors for entirely different types of systems (i.e., the large dataset of Peverati and Truhlar [2]). While the study raises many interesting questions, it did not in fact compare the accuracy of functionals for reproducing both the energies and the electron densities of the same materials. So, any conclusions about how one functional gets the energies better but the electron densities worse are limited by the fact that those measures were quantified for entirely different classes of materials.

Specifically, we do not know whether the functionals that got the energies better for molelcules performed better or worse for the electron densities of those materials, because that was never measured. Moreover, we do not know whether the functionals that performed better for the electron densities of the isolated closed-shell atoms and atomic cations performed better or worse for the energies of those materials, because that data was not reported.

The study has shown is that some functionals, which perform better for electron density of one type of system have also performed worse for the energies of other types of systems. However, I think the study has serious limitations because the energies and electron densities were not compared for the same systems. Nonetheless, it raises some interesting questions that should be explored in future studies. Specifically, do the recent functionals that perform well for molecules and solids get the electron density distributions for those materials more or less accurately than the earlier functionals?

[1] M. G. Medvedev, I. S. Bushmarinov, J. Sun, J. P. Perdew, and K. A. Lyssenko, Science 355 (2017) aah5975.

[2] R. Peverati, D. G. Truhlar, Philos. Trans. R. Soc. A 372 (2014) 20120476.

Tom

Hi Susi,

Thanks for pointing that out. I agree with many of your critiques on the Science article.
It would be interesting if someone would do a more rigorous study comparing more functionals with proper comparisons of both energies and electron distributions for a diverse set of materials.
One of the things that I struggle with is that with so many newly developed DFT functionals in recent years, I have no idea which of them actually perform well across diverse materials.
A study that compares not only energetics, but also computed electron densities, across diverse materials (molecules, solids, transition states, etc.) could be extremely valuable for figuring out which recently developed functionals actually perform well.

One of the things the Science article claims is that the recent functionals are getting worse on the electron densities, but as you have pointed out, we don't necessarily know whether this is truly the case. Particularly, because the Science article tested such a limited set of materials (i.e., single closed shell atoms and atomic cations) for the densities but cited energies for entirely different material types, and as you pointed out the functionals tested omitted many recent approaches developed by diverse research groups.

It would be great if someone could do a more rigorous and inclusive study.

Tom

On Thu, Jan 26, 2017 at 2:56 PM, Susi Lehtola susi.lehtola * alumni.helsinki.fi <owner-chemistry##ccl.net> wrote:

Sent to CCL by: Susi Lehtola [susi.lehtola---alumni.helsinki.fi]
On 01/26/2017 10:16 AM, Thomas Manz thomasamanz_._gmail.com wrote:

A recent issue of Science contained an interesting article "Density
functional theory is
straying from the path toward the exact functional"[1].

This has already been discussed on the list in the thread
"DFT discovers it's recapitulating QSAR"

I'd like to repeat my arguments in
http://www.ccl.net/cgi-bin/ccl/message-new?2017+01+06+006

that you could rewrite the result of the study as a much less catching "Minnesota functionals fail to reproduce electron density in small atoms and cations"
--
-----------------------------------------------------------------------
Mr. Susi Lehtola, PhD Chemist Postdoctoral Fellow
susi.lehtola|-|alumni.helsinki.fi Lawrence Berkeley National Laboratory
http://www.helsinki.fi/~jzlehtol USA

作者
Author: yangyinuo823 时间: 2017-2-15 16:04
平常用的基本都是b3lyp和m06系列的，求科普perdew的原理派一般常用到的有哪些方法，以及适用于哪些体系？

作者
Author: sobereva 时间: 2017-2-15 18:03

yangyinuo823 发表于 2017-2-15 16:04
平常用的基本都是b3lyp和m06系列的，求科普perdew的原理派一般常用到的有哪些方法，以及适用于哪些体系？

perdew搞的那些在分子体系已经不太常用，因为有明显更好的选择。在周期性体系用得较多，特别是PBE，是周期性计算最常用的。

作者
Author: yangyinuo823 时间: 2017-2-17 16:26

sobereva 发表于 2017-2-15 18:03
perdew搞的那些在分子体系已经不太常用，因为有明显更好的选择。在周期性体系用得较多，特别是PBE，是 ...

谢谢sob老师！

作者
Author: captain 时间: 2017-6-9 10:12
在做报告呢

作者
Author: meatball1982 时间: 2017-6-10 11:07
看了一下，挺有意思的，后续的两个文献。

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