User talk:Droog Andrey
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For those of us who don't know what they are, could you add pages for Breedsma and Ragisma? Rigadoun (talk) 01:44, 3 July 2007 (UTC)
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Thank you
[edit]I am really glad you've resumed the group 3 dispute. I have indeed had the feeling that the previous disputes on the matter were not entirely complete---not just because I prefer your opinion as well, even though I actually do---because it seemed to me not all arguments had been taken in account equally. Thank you for dropping by; if your stay in our project lasts longer, please feel welcome.--R8R (talk) 04:12, 26 February 2018 (UTC)
Yellow colour of caesium
[edit]I wonder what happens for francium when relativistic effects should really be important. ^_^ If the transition involved is the ns–np one to the first excited state then we can look up the energy levels and see that the transition energy is closer to that of Rb than that of Cs, which would predict a silvery colour again; is that simplistic analysis correct? Double sharp (talk) 04:13, 8 April 2018 (UTC)
- @Double sharp: are you sure that yellow colour is related to relativistic effects indeed? Droog Andrey (talk) 08:56, 8 April 2018 (UTC)
- No, I didn't mean that the yellow colour of Cs is related to relativistic effects; the plasmonic frequency of Cs (going into the visible range) quite nicely continues the trend down the group (10.1103/PhysRev.44.353), and relativistic effects shouldn't be that big around Z ~ 50 (they're not big for Ag either, which is silvery). I was asking for Fr, for which relativistic effects should really be important. ^_^ Double sharp (talk) 10:07, 8 April 2018 (UTC)
- @Double sharp: ns–np gap should increase for Fr compared to Cs, but I think that's not about the colour. The plasmonic frequency for Fr metal could be right on the edge of visible spectrum, making it pale yellow. Droog Andrey (talk) 03:59, 9 April 2018 (UTC)
- Interesting (and perhaps coincidentally not too different from what the ns–np gap explanation would have us guess, which interpolating between Rb and Cs at least leaves the possibility of a pale yellow colour open). Do you know where I can find values for the plasmonic frequencies of the rest of the metals? Double sharp (talk) 04:04, 9 April 2018 (UTC)
- @Double sharp: unfortunately, I've never seen tabulated values across all the metals. Droog Andrey (talk) 20:44, 9 April 2018 (UTC)
- OK, looks like it's time for me to start trying to collect them. ^_^ Double sharp (talk) 03:56, 11 April 2018 (UTC)
- @Double sharp: unfortunately, I've never seen tabulated values across all the metals. Droog Andrey (talk) 20:44, 9 April 2018 (UTC)
- Interesting (and perhaps coincidentally not too different from what the ns–np gap explanation would have us guess, which interpolating between Rb and Cs at least leaves the possibility of a pale yellow colour open). Do you know where I can find values for the plasmonic frequencies of the rest of the metals? Double sharp (talk) 04:04, 9 April 2018 (UTC)
- @Double sharp: ns–np gap should increase for Fr compared to Cs, but I think that's not about the colour. The plasmonic frequency for Fr metal could be right on the edge of visible spectrum, making it pale yellow. Droog Andrey (talk) 03:59, 9 April 2018 (UTC)
- No, I didn't mean that the yellow colour of Cs is related to relativistic effects; the plasmonic frequency of Cs (going into the visible range) quite nicely continues the trend down the group (10.1103/PhysRev.44.353), and relativistic effects shouldn't be that big around Z ~ 50 (they're not big for Ag either, which is silvery). I was asking for Fr, for which relativistic effects should really be important. ^_^ Double sharp (talk) 10:07, 8 April 2018 (UTC)
Illustrated atomic radii on your periodic table
[edit]Do you have the original atomic radii values that are presented as differently sized spheres in your periodic table? It would be nice to collect those too as we don't have a single set covering all 118 elements at Atomic radii of the elements (data page). Double sharp (talk) 04:00, 11 April 2018 (UTC)
- @Double sharp: they are taken from 10.1002/chem.200800987 :) Droog Andrey (talk) 09:18, 13 April 2018 (UTC)
- P.S. They've been already tabulated here Droog Andrey (talk) 09:22, 13 April 2018 (UTC)
- I thought it might have been that, but initially dismissed that due to some differences, like for cerium (which is quite small in the paper). Is that one because your table is using its trivalent rather than tetravalent radius? Double sharp (talk) 09:31, 13 April 2018 (UTC)
- @Double sharp: single-bond radii were used, and indeed, there was an adjustment for Ce (176 instead of 163) and for O-F-Ne (don't remember the exact values). Droog Andrey (talk) 09:49, 13 April 2018 (UTC)
- I thought it might have been that, but initially dismissed that due to some differences, like for cerium (which is quite small in the paper). Is that one because your table is using its trivalent rather than tetravalent radius? Double sharp (talk) 09:31, 13 April 2018 (UTC)
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[edit]A little update for your dications page
[edit]New article: looks like we have Ds2+ 6d67s2, Rg2+ 6d77s2, Cn2+ 6d97s1 (predicted, of course). Double sharp (talk) 12:56, 31 March 2020 (UTC)
Just wondering re group 12
[edit]Is there much hope for getting Zn, Cd, and Hg in oxidation states above +2? I know Zn(AuF6)3 has been suggested, but it may be thermochemically unstable and not really Zn(III) anyway (10.1021/ja3052409). Double sharp (talk) 12:17, 7 April 2020 (UTC)
- Brought to the reference desk as well. Double sharp (talk) 05:04, 9 April 2020 (UTC)
Thanks to one of your old articles on your website
[edit]We now have a section Periodic table#Kainosymmetry. ^_^ Double sharp (talk) 05:44, 17 May 2020 (UTC)
Metallicity: copernicium and oganesson
[edit]If Og is expected to be a semiconductor, then should it not be classified as a nonmetal by your definition? It would lack a Fermi surface. And I guess copernicium as an insulator has to be taken out of metals too. Do you have plans to update your poster (and I guess for helium 3.20 also), or is my analysis incomplete? Double sharp (talk) 12:59, 21 July 2020 (UTC)
- @Double sharp: EN for He will be updated, of course. As for metallicity, I'd rather wait for more computations. My intuition suggests that Og should be a metal; still have no idea for Cn. Droog Andrey (talk) 17:14, 21 July 2020 (UTC)
- Fair enough. The superheavies are weird, I will wait. For now my userpage periodic table calls Cn and Og nonmetals since I have not enough chemical intuition for these, but as more computations come I will change it,
- Since we are talking about metallicity again; I understand that antimony is normally classified as a metal in Russian schoolbooks, and that you have made some changes to your poster in the past to avoid conflict with them (i.e. not calling Cu2+ amphoteric). (For that reason I don't expect to see helium over beryllium any time soon; fixing group 3 is way more important for consistency. ^_^) Now, I understand that for that one there are obviously also chemical reasons, as the formation of [Cu(OH)4]2− has more to do with complex formation than acidity. So I wanted to ask it this way: if you were writing it for yourself without such a constraint, would you rather call antimony a metal or a nonmetal?
- I currently think the fact that its chemistry seems on the border means that calling in the physical fact that it isn't a true metal may not be so bad. OTOH, mostly Sb alloys are metallic in conductivity, that is also something. If we exclude Sb from metals, the metal-nonmetal line goes forward by one when there's no contraction (Be to Al, Ga to Sn), stays put when there is one (Al to Ga), goes forward two for the first row when we lose both kainosymmetry and instantly gain significant shielding, and then runs away almost to the end in period 6 due to 6p3/2 expansion. Cationic chemistry seems a bit orthogonal to the idea; after all rhenium is a metal, no one doubts it even with less real aqueous cations than antimony, so it is not necessary, and if Ge2+ really exists then it is not even sufficient. But I don't know how much is best to weight these things. Double sharp (talk) 09:28, 22 July 2020 (UTC)
- @Double sharp: I'd rather call it a metal. Otherwise some questions about beryllium and so on will rise. Droog Andrey (talk) 19:08, 22 July 2020 (UTC)
- Wow, I didn't know beryllium had semimetallic properties. That is cool indeed. I suppose Be is maybe a bit more clearly on the metallic side chemically than Sb, but indeed I'd rather keep criteria to a minimum.
- Just one more question before I maybe take a break from these issues then. ;) Regarding how I used to show "weak nonmetals" {H, B, C, Si, P, Ge, As, Se, Te}, "strong nonmetals" {N, O, F, S, Cl, Br, I}, "noble nonmetals" {He, Ne, Ar, Kr, Xe, Rn} (let's ignore period 7 for this): do you think this sort of thing is a useful generalisation attempt? I mostly was inspired by Gary Wulfsberg's Principles of Descriptive Inorganic Chemistry for it, but as you noted it's not just electronegativity, there is also oxidising power, electron affinity, and the physical metal-nonmetal distinction. And do you think there's anything in trying to extend this combination of properties to metal-nonmetal dichotomy and maybe to separate stronger and weaker classes of metallic elements, or is it better to treat the metals vs nonmetals topic in the physical way mostly only? Double sharp (talk) 14:25, 24 July 2020 (UTC)
- Never mind, I think I answered my own question. Metal-nonmetal difference seems more a simple substances thing than an element thing. ^_^
- I guess grey tin is not a problem as the band gap is zero. ;) Double sharp (talk) 13:51, 26 July 2020 (UTC)
- @Double sharp: I'd rather call it a metal. Otherwise some questions about beryllium and so on will rise. Droog Andrey (talk) 19:08, 22 July 2020 (UTC)
Notice of Dispute resolution noticeboard discussion
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This message is being sent to let you know of a discussion at the Wikipedia:Dispute resolution noticeboard regarding a content dispute discussion you may have participated in. Content disputes can hold up article development and make editing difficult for editors. You are not required to participate, but you are both invited and encouraged to help this dispute come to a resolution. The thread is "Periodic table".The discussion is about the topic Periodic table.
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Notice of Dispute resolution noticeboard discussion
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This message is being sent to let you know of a discussion at the Wikipedia:Dispute resolution noticeboard regarding a content dispute discussion you may have participated in. Content disputes can hold up article development and make editing difficult for editors. You are not required to participate, but you are both invited and encouraged to help this dispute come to a resolution. The thread is "Periodic table".The discussion is about the topic Periodic table.
Please join us to help form a consensus. Thank you!
--Double sharp (talk) 08:36, 4 August 2020 (UTC)
Re your periodic table poster: atomic weights
[edit]In conjunction with your next update of helium EN to 3.20, I think a few atomic weights may need updates to latest IUPAC values. Also, IUPAC now gives intervals for atomic weights of some elements. Where only a single value is needed, they give conventional values with few significant figures. That would suggest the following changes (I guess 6 s.f. are used when more are known):
- Hydrogen: 1.008
- Lithium: 6.94
- Boron: 10.81
- Carbon: 12.011
- Nitrogen: 14.007
- Oxygen: 15.999
- Magnesium: 24.305
- Silicon: 28.085
- Sulfur: 32.06
- Chlorine: 35.45
- Argon: 39.95
- Germanium: 72.630 (maybe last figure can be dropped, ±0.008 uncertainty)
- Selenium: 78.971 (maybe last figure can be dropped, ±0.008 uncertainty)
- Molybdenum: 95.95
- Technetium: better 97, since NUBASE2016 says Tc-97 is a bit more stable than Tc-98
- Cadmium: 112.414
- Ytterbium: 173.045 (but this is ±0.010, so maybe should round off)
- Mercury: 200.592
- Thallium: 204.38
- Seaborgium: better 269, this isotope is more stable (10.1103/PhysRevC.97.014320) with half-life 14+10
−4 minutes compared to 2.4 min for 271 - Bohrium: better 270, more stable than 274 per NUBASE2016
- Moscovium: better 290 per NUBASE2016
I don't mention cases where last figure accords but has some uncertainty. ;) And maybe I have not the latest atomic data for this, this is just latest I have. Double sharp (talk) 13:16, 14 August 2020 (UTC)
- @Double sharp: thanks a lot. I'm aware of that data, it's just difficult to make these corrections in png (original pdf is gone because of file system failure). Droog Andrey (talk) 16:35, 14 August 2020 (UTC)
- Ah, I see. Take your time, please, there's no rush. Just please do tell me when the corrected version is up, as I like having your table to link to. ;)
- I guess this way it will be hard to put 119 up when it hopefully comes next year. Or do you still plan to ignore it and the next ones for a while as I think you said the last time? Maybe that's a shame, as following something R8R said back in 2018, 119 would not really be less worthy than Og.
- I also heard about the situation in your country. Hopefully you're safe and fine. Double sharp (talk) 05:32, 15 August 2020 (UTC)
- The same goes from me. I hope you're safe and I hope it stays this way.--R8R (talk) 15:10, 15 August 2020 (UTC)
- Thank you guys, I'm just fine. Droog Andrey (talk) 19:33, 19 August 2020 (UTC)
- Great to hear. I admit, I got a little worried when you didn't reply for a few days. ^_^ Double sharp (talk) 03:52, 20 August 2020 (UTC)
- Thank you guys, I'm just fine. Droog Andrey (talk) 19:33, 19 August 2020 (UTC)
- The same goes from me. I hope you're safe and I hope it stays this way.--R8R (talk) 15:10, 15 August 2020 (UTC)
7th period element melting points
[edit]If you are all right (which I hope you are), there is a little question I have wondered about in passing and forgot to ever ask.
What states of matter do you think the 7th period elements should be in at standard conditions? (Or "close enough" since Cs and Ga have melted by 30°C.) I ask because lots of periodic tables I remember having seen IRL "cop out" and classify solid/liquid/gas/synthetic(!), which seems a bit lame to me.
I admit my first instinct was to colour Fr, Cn, Fl liquid (along with Hg, Cs, Ga) and leave the rest solid (I don't think oddities like the Ga structure would recur, but you never know, maybe for Ts), but I confess I don't know enough to answer it well and therefore ask you. ;) Double sharp (talk) 09:14, 18 August 2020 (UTC)
- @Double sharp: I'd rather suppose only Cn and Fl to be liquid at RT. Fr should go above Cs, and Ts should melt well beyond 100°C I think. Droog Andrey (talk) 19:38, 19 August 2020 (UTC)
- Thank you! I suppose for Fr it is due to 7s contraction? Out of curiosity (and of course a desire to learn more) I'd like to know how you got the estimate for Ts. ;) Double sharp (talk) 03:03, 20 August 2020 (UTC)
- @Double sharp: Yes, relativistic contraction for Fr and large polarizability for Ts (much larger than for gallium or iodine). Droog Andrey (talk) 06:14, 20 August 2020 (UTC)
- Again, thank you! I see there are polarisability values for everybody but Lv at 10.1080/00268976.2018.1535143. So, higher polarisability strengthens metallic bonding? Makes sense to my high-school intuition (greater electrostatic attraction, but obviously not so much that delocalisation itself gets hard, which maybe affects f elements), although no doubt it is really more complicated. Maybe there is after all a good explanation for the melting points in group 2 that Chemguide threw its hands up in the air for. XD Double sharp (talk) 07:21, 20 August 2020 (UTC)
- Polarizability itself does not strengthen metallic bonding. After all, metallic bonding strength affects boiling points, not melting ones. Polarizability of Ts matters if we suppose diatomic structure analogous to gallium or iodine. If metallic Ts is just fcc, then its melting point is even higher. Droog Andrey (talk) 07:02, 21 August 2020 (UTC)
- I see, thank you for the explanation. Now indeed kicking myself for forgetting the basic high-school knowledge that metallic bond only fully breaks at boiling, not melting. XD
- I hope you do not mind my questions, because I want my understanding to be as correct as possible. So, how does melting Ga work exactly? Is it more or less like iodine where it is just about overcoming weaker interactions between Ga2 molecules, or is that a too naïve view? And is there a way to guess melting points from the structure of a metal? Double sharp (talk) 07:12, 21 August 2020 (UTC)
- It's very non-trivial to guess melting points in general case. For Ga the key might be interaction strengthening in more dense liquid state (you see, electrical resistance falls upon melting). Droog Andrey (talk) 09:16, 21 August 2020 (UTC)
- Many thanks! And can I ask you, is the explanation at Gallium#Physical properties for the low melting point right? I put it in I think in 2016 from reading Greenwood and Earnshaw, but they qualified it with a "may". Double sharp (talk) 10:31, 21 August 2020 (UTC)
- Yes, I think it's at least partial explanation. Droog Andrey (talk) 18:04, 21 August 2020 (UTC)
- Fantastic. Many thanks for all your answers. ^_^ Double sharp (talk) 02:53, 22 August 2020 (UTC)
- Yes, I think it's at least partial explanation. Droog Andrey (talk) 18:04, 21 August 2020 (UTC)
- Many thanks! And can I ask you, is the explanation at Gallium#Physical properties for the low melting point right? I put it in I think in 2016 from reading Greenwood and Earnshaw, but they qualified it with a "may". Double sharp (talk) 10:31, 21 August 2020 (UTC)
- It's very non-trivial to guess melting points in general case. For Ga the key might be interaction strengthening in more dense liquid state (you see, electrical resistance falls upon melting). Droog Andrey (talk) 09:16, 21 August 2020 (UTC)
- Polarizability itself does not strengthen metallic bonding. After all, metallic bonding strength affects boiling points, not melting ones. Polarizability of Ts matters if we suppose diatomic structure analogous to gallium or iodine. If metallic Ts is just fcc, then its melting point is even higher. Droog Andrey (talk) 07:02, 21 August 2020 (UTC)
- Again, thank you! I see there are polarisability values for everybody but Lv at 10.1080/00268976.2018.1535143. So, higher polarisability strengthens metallic bonding? Makes sense to my high-school intuition (greater electrostatic attraction, but obviously not so much that delocalisation itself gets hard, which maybe affects f elements), although no doubt it is really more complicated. Maybe there is after all a good explanation for the melting points in group 2 that Chemguide threw its hands up in the air for. XD Double sharp (talk) 07:21, 20 August 2020 (UTC)
- @Double sharp: Yes, relativistic contraction for Fr and large polarizability for Ts (much larger than for gallium or iodine). Droog Andrey (talk) 06:14, 20 August 2020 (UTC)
- Thank you! I suppose for Fr it is due to 7s contraction? Out of curiosity (and of course a desire to learn more) I'd like to know how you got the estimate for Ts. ;) Double sharp (talk) 03:03, 20 August 2020 (UTC)
Gotta add Sigma-Aldrich to the list of periodic table makers that made the wrong decision on Fr. Although since atomic radius of Fr is between Cs and Rb (which melts at 39°C), I guess they might get away with claiming that they had a really hot "room temperature" in mind. ;) Double sharp (talk) 12:33, 1 March 2021 (UTC)
Paper on electronegativities
[edit]Hello, this came up at WT:ELEM a while ago, and I thought you'd be interested: what do you think of this paper by Karol? Double sharp (talk) 22:04, 5 October 2020 (UTC)
- Sadly, nothing interesting. Droog Andrey (talk) 07:58, 6 October 2020 (UTC)
- Thank you! I admit I wasn't too impressed with those values either, but it's great to get confirmation from you. ^_^ Double sharp (talk) 11:13, 6 October 2020 (UTC)
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Might interest you
[edit]Paper (containing calculations for the E140 isoelectronic sequence). Seems like indeed we transition from open-shell 5g at 1422+, to closed-shell at 1433+. From 1433+ on, configuration we get is closed shell [Og]8s25g188p2. Since 8p should not be drowned yet at the start, maybe we get two-too-high oxidation states compared to the actinoid congeners then? Double sharp (talk) 09:50, 18 February 2021 (UTC)
- @Double sharp: Yes, too-high oxidation states are possible here, that's why I proposed 2x18 footnote for 5g186f148s28p2. The article is interesting, but I doubt about early 8p3/2 occupation. Droog Andrey (talk) 19:46, 24 February 2021 (UTC)
- Do you think the 2×18 footnote is better, or the form we currently have with 143–156 assigned to an f series because of the g subshells presumably being last active at 142?
- If I read and understand your older popularisation article correctly, we should probably have 121–124 acting like first four actinoids (maybe more active still), followed by a bunch of copycats of uranium-like behaviour as the 5g fills underneath. Perhaps with +4 becoming more important than +6 as 8s2 falls into the core later in this series, and then rising again for 143++, before 8p1/2 also sinks into core at 150-ish and we start to see same fall as late actinoids. But how good, say, do you think would be homologies between things like 121 and 139 (from top row to bottom?). Double sharp (talk) 08:13, 25 February 2021 (UTC)
- I don't know for sure which form is better. Some further calculations are really needed there :) Droog Andrey (talk) 05:03, 1 March 2021 (UTC)
Copernicium again
[edit]Do you think something like this for Hg might be going on also for Cn? Double sharp (talk) 13:58, 26 February 2021 (UTC)
- Yes, it might be :) Droog Andrey (talk) 04:52, 1 March 2021 (UTC)
Huh, apparently some new calculations got published for Cn: [1]. Again predicting a dispersion-bound noble liquid, and also claiming that 6d > 7s order suppresses metallic bonding. (Which I don't get, admittedly as a layman here. Shouldn't 6d expansion rather favour metallic bonding? Early 6d metals like Sg surely have 6d > 7s order too. How far away is 7p1/2, too; could it play a role?)
I must admit, I'm surprised at large liquid range calculated for a supposedly dispersion-bounded solid in the new work (PBE-D3, mp −47°C, bp 88°C). With PBEsol (which they say is better suited for metallic systems) the range is smaller (mp 11°C, bp 67°C), but still seems large for me (just as a layman here) comparing with Rn (mp −71 °C, bp −62 °C). However it does seem intermediate between Rn and Hg (mp −39 °C, bp 357 °C) in a way I could get behind. Are the extra electrons and relativity that effective? Well, they agree Fl is a metal (same paper, citing this older one), with predicted mp −73°C (lower than Cn!), bp 107°C (though they say to take it with a grain of salt). Interestingly similar to what you wrote at the end of this old section, with Cn barely more volatile than Hg, and Fl well more volatile but still a liquid. They both seem somehow "on the way" on the transition from dispersion forces to metallic bonding, with Cn closer to Rn and Fl closer to Hg. ;)
Though my high-school chemical intuition still wonders if, even if Cn might be dispersion-bounded, it might not be pushed to engage in metallic interactions when alloyed with somebody else as suggested by Eichler here. ;) Double sharp (talk) 09:42, 1 March 2021 (UTC)
- I think 6d is a bit too short for metallic bonding, while 7p1/2 should play a key role. I'd like to look at Cn-Hg phase diagram :) Droog Andrey (talk) 14:05, 1 March 2021 (UTC)
- Quite interesting considering doi:10.1103/PhysRevLett.72.2446 (attributing structure changes down group 12 to relativity increasing s-p hybridisation). I guess I am willing to provisionally believe in metallic copernicium now. ;) Double sharp (talk) 04:22, 7 March 2021 (UTC)
Chromium
[edit]Hi, do you have a source for what you wrote on your website "например, хром долгое время считался одним из самых твёрдых металлов, но, когда его научились глубоко очищать, обнаружилось, что хром пластичен"? It really would be something amazing to point out when whistle-stop describing metals. ;) Double sharp (talk) 04:08, 7 March 2021 (UTC)
- Most of russian secondary sources give that, but I still haven't found any primary ones. Droog Andrey (talk) 08:41, 19 March 2021 (UTC)
Weakest metals
[edit]I think I remember you saying that Sb chemically is pretty much on the edge between metals and nonmetals. So I want to ask you where you think At is. ;) Double sharp (talk) 06:55, 19 March 2021 (UTC)
I think At (compared to Sb) is closer to metals as simple substance, but closer to nonmetals in compounds :) Droog Andrey (talk) 08:40, 19 March 2021 (UTC)
- Thanks! :) Double sharp (talk) 08:54, 19 March 2021 (UTC)
BTW, I remember that on your PT poster At used to be a nonmetal. Can I ask why you thought so then? :) Double sharp (talk) 15:39, 19 March 2021 (UTC)
- That's because I was aware only of scalar-relativistic calculations :) Droog Andrey (talk) 16:55, 19 March 2021 (UTC)
- I see. ;) Like this guy I still hope for more calculations. Double sharp (talk) 04:06, 20 March 2021 (UTC)
- And I see you corrected He, thanks! ;) Double sharp (talk) 15:46, 19 March 2021 (UTC)
Regarding amorphous metals: seems by doi:10.1016/0022-3093(93)90768-S that amorphous Sb is only a semiconductor (while Bi is a metal), but that by constraining it to match Bi short-range structure amorphous Sb can be metallised anyway. Still kinda OK for the weak metal, I guess?
For silicon much pressure is needed. Double sharp (talk) 16:00, 30 March 2021 (UTC)
- I think that's OK. Droog Andrey (talk) 20:51, 3 April 2021 (UTC)
BTW, can I ask why astatine had much higher EN of 2.30 on your chart in 2018? Double sharp (talk) 09:59, 11 April 2021 (UTC)
- The same answer really: scalar-relativistic calculations :) Droog Andrey (talk) 19:22, 11 April 2021 (UTC)
A couple of questions for you
[edit]Hi DA, I have a couple of questions about something you wrote in 2018:
- What did you mean about the reverberation of secondary periodicity from Na to K? (Is it because Li is above a 1s2 core whereas the other ones are above an ns2np6 core which shields a bit worse? This is the only thing I could find, pages 17 through 19. I admit that trend H-Li-Na-K, He-Be-Mg-Ca in electronegativity seems somehow to have similarity to F-Cl-Br-I or Ne-Ar-Kr-Xe, maybe the more so in those cases with reversed electronegativity order where Li becomes more electropositive than Na.)
- What criterion would you use to decide the fate of s-elements, since it is the only block for which the idea "look at highest angular momentum subshell" does not work? (Myself, I would take the cases "one valence electron" and "two valence electrons" separately as you suggest, but seeking some confirmation XD.)
P.S. I suppose the problem is not just group 2, because np orbitals should definitely be active in Li–Fr and Be–Ra. Double sharp (talk) 09:31, 2 April 2021 (UTC)
- K has much larger core, and therefore higher polarizability than Na. The same occurs for Cs and Rb. So we have electropositivity jumps from odd to even period for s-elements. And, yes, I'd rather choose "≤ 2 valence electrons" for s-elements :) Droog Andrey (talk) 11:49, 3 April 2021 (UTC)
- Huh, that's cool. Didn't know that, thanks. Why does it happen? Just comparing the previous noble gases, I see that He is tiny, Ne is a bit less tiny but not too much larger, and then suddenly Ar is a lot larger. Sort of suggests to me lack of kainosymmetry from Ar onwards, but then what's going on for Kr vs Xe? The 3d contraction hurting Kr maybe? I'd guess what is correct for He through Xe series should also be correct for Li+ through Cs+ series. XD
- Is electropositivity meant in the sense I know from high school (opposite of electronegativity), or something a bit different? Because on your scale series H–Cs and He–Ba are monotonic electronegativity decreases.
- So it seems to me that even periods in s block behave as odd periods in other blocks and vice versa. Seems maybe an argument for Janet table, isn't it LOL. Particularly so if 3d contraction is responsible for size not going up so much between K+ and Rb+. XD (Not being very serious here, since the big energy gap (n−1)p << ns seems like a much more relevant argument.)
- Will 7p elements be a problem? 7s is a bit doubtfully valent for flerovium, isn't it? I don't think we can really speak of Fl through Og as 4 through 8 valence electrons. Are we just going to just take ns2 npx at its word? Subtracting 2 from column numbers might work to account for preemptive filling of s orbitals in each case, except I'm not sure 7p1/2 is actually valent at Ts and Og. Or maybe just ignore spin-orbit problem, LOL. XD
- Sorry that two questions spiral into many. XD Double sharp (talk) 13:34, 3 April 2021 (UTC)
- Well, I guess I could answer this to my satisfaction mostly: big energy gap (n-1)p << ns is more important than weak s-block secondary periodicity, because it gives chemically important noble-gas situation. So, easier to just remember that s-block really represents the previous n+l value; it was an exception for preemptive ns2 filling, so it can be an exception for even-odd rule too. :) As for superheavies: classification is basically partly done for pragmatism (just like how in mathematics it was eventually decided not to call units primes mostly), so a slight approximation is allowable. They are also exceptions to even-odd rule, but for the most part noble gas configuration still exists as a thing (I mean, maybe Uue can breach the shell for some oxidising compounds, but that should really be it I think). Double sharp (talk) 06:34, 12 April 2021 (UTC)
New electronegativity scale
[edit]What think you of this? (I find it step in correct direction from Pauling for things like tungsten, but lanthanoid values here seem very off.) Double sharp (talk) 06:48, 12 April 2021 (UTC)
- Looks interesting in spite of some issues like N > Cl, Se > I, or Hg > Po :) Droog Andrey (talk) 09:26, 13 April 2021 (UTC)
- Another approach BTW: 10.1021/acsomega.0c00256 Droog Andrey (talk) 09:09, 19 April 2021 (UTC)
- By the way, why do you think that N < Cl although hydrolysis of NCl3 gives NH3 and HOCl? Burzuchius (talk) 09:37, 23 August 2022 (UTC)
- Hydrolysis is not a good criterion since NOCl gives HNO2. Droog Andrey (talk) 14:32, 23 August 2022 (UTC)
- Thank you for your answer. Burzuchius (talk) 19:15, 23 August 2022 (UTC)
- Hydrolysis is not a good criterion since NOCl gives HNO2. Droog Andrey (talk) 14:32, 23 August 2022 (UTC)
- By the way, why do you think that N < Cl although hydrolysis of NCl3 gives NH3 and HOCl? Burzuchius (talk) 09:37, 23 August 2022 (UTC)
8s elements
[edit]Just curious: predictions in WP articles are given as (Pauling) 0.86 for Uue, 0.91 for Ubn. Do you find that plausible? (It would put Uue as less electropositive than K, but Ubn as between Sr and Ba. Well maybe, given reversal seems to hit Fr more than Ra...)
Also, given lower 7p to 8s gap, might they not also have some similarity to IB and IIB groups? Double sharp (talk) 10:36, 12 April 2021 (UTC)
- Hmm, not too different from Karol's I see. Of course his values for 7p are not interesting because 7s is hardly valent there, but maybe the 8s values are less bad I guess. Double sharp (talk) 09:59, 13 April 2021 (UTC)
OK, somewhat disappointingly the predictions seem to still fall into a black hole after Ubn. I think I would guess something like (on your scale) Uue 0.82, Ubn 0.93, Ubu 0.96, Ubb 0.99 maybe to start the eighth row. After that, probably massive collision among all the other assigned ones in 4f and 5f. Dunno if the usual half-row situation (like Mn/Zn, Eu/Yb) would do anything at Ube at this point; I guess 8th row blocks should be too blurred to make much difference. Double sharp (talk) 11:44, 13 April 2021 (UTC)
More stuff from 2018
[edit]In Wikipedia talk:WikiProject Elements/Archive 35#Solid state physics, you wrote:
“ | I'd say the chemistry of antimony is right on the edge between metallic and nonmetallic. I'd even say that there's some kind of parallel between Sb and Re (both are just before the middle of the block). Yes, white phosphorus is metastable as well as diamond, for example, but they are both much more stable than black antimony. | ” |
So, just curious re what parallels between Sb and Re you meant. :)
- Curiously, I don't remember what exactly I had in mind. Maybe that was the nature of chemical bonds in highest oxidation state. Droog Andrey (talk) 15:00, 30 July 2021 (UTC)
Double sharp (talk) 08:42, 19 April 2021 (UTC)
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[edit]Flerovium
[edit]A new paper suggests semiconducting Fl(!). Double sharp (talk) 18:45, 22 August 2022 (UTC)
- Thanks for that, I'll take a look :) Droog Andrey (talk) 18:54, 22 August 2022 (UTC)
- Although recently published experiments now say it's probably a volatile metal (metallic interpretation, because a noble gas would not deposit on Au at room temperature). Seems like Cn and Fl metallicity are both highly underestimated by calculations compared to experiments, and I wonder why. (I thought it might have been 7p SO splitting being bigger than thought, but while that would indeed make Cn more metallic, it'd make Fl less so, so that doesn't work.) Double sharp (talk) 23:02, 9 October 2022 (UTC)
- It's quite difficult to calculate metallicity. Chemical intuition suggests that Cn and Fl should be volatile metals indeed. However, I'd expect Cn a bit more volatile than Fl :) Droog Andrey (talk) 08:02, 10 October 2022 (UTC)
- Interesting, I wonder why? In 2018 I think you had the opposite opinion. :) Double sharp (talk) 22:43, 5 November 2022 (UTC)
- I guess because of larger atomic radius of Fl. Droog Andrey (talk) 11:54, 15 November 2022 (UTC)
- Interesting, I wonder why? In 2018 I think you had the opposite opinion. :) Double sharp (talk) 22:43, 5 November 2022 (UTC)
- It's quite difficult to calculate metallicity. Chemical intuition suggests that Cn and Fl should be volatile metals indeed. However, I'd expect Cn a bit more volatile than Fl :) Droog Andrey (talk) 08:02, 10 October 2022 (UTC)
- Although recently published experiments now say it's probably a volatile metal (metallic interpretation, because a noble gas would not deposit on Au at room temperature). Seems like Cn and Fl metallicity are both highly underestimated by calculations compared to experiments, and I wonder why. (I thought it might have been 7p SO splitting being bigger than thought, but while that would indeed make Cn more metallic, it'd make Fl less so, so that doesn't work.) Double sharp (talk) 23:02, 9 October 2022 (UTC)
Interesting new article from Scerri
[edit]Hi Droog Andrey, what do you think of this? Double sharp (talk) 22:36, 5 November 2022 (UTC)
- Quite interesting indeed. There could be more arguments for He above Be, you know :) Droog Andrey (talk) 11:57, 15 November 2022 (UTC)
- I'd like to see them! I know many are in Grochala (2018) and Kurushkin (2020). I haven't been able to find a copy of Henry Bent's book, but his daughter wrote an article. But I'd really like to find more differences between He and heavier noble gases. I have wondered if superfluid/supersolid phenomena for He are related to the spherical 1s. (I mean, obviously Ne is solid at the relevant temperatures, which is why looking at supersolids might be more fruitful.)
- To me, the definitive argument is the way Scerri referred to QM in this article. The PT is an expression of the quantum-mechanical laws, not the final chemistry that is many steps removed from it. So not even Ptolemy vs Copernicus, but Ptolemy vs Newton, in a sense.
- What do you think of Scerri's support for the Janet (fdps) table with the s-block on the right edge? My general impression is that within-block trends look better with Janet (fdps) because then ℓ changes monotonically and first-row anomaly / secondary periodicity consistently follows the n+ℓ parity difference (including s-block directly for 1s vs 2s, and in the sense of cores and thus polarisability for 3s vs 4s and 5s vs 6s); but between-block trends across the period look better with the standard sfdp because the energies of ns orbitals are closer to those of the next n+ℓ group, so the natural trend (e.g. atomic radius) goes from group 1 to group 18. Relativistic shrinking of np3/2-(n+1)s gap would muddy that for the period divide from Og to 119, e.g. 7p-8s hybridisation in LvH2, but I think that is too weak a reason. But maybe one should just think of the PT as a spiral (to preserve the increasing Z order), and just view fdps and sfdp as cutting it in two different places. Double sharp (talk) 19:11, 17 November 2022 (UTC)
It's kind of old, but Jensen wrote a pretty good article on periodicity for Britannica On-Line 2000. (Though his opinion then was that Zn, Cd, and Hg don't use d-orbitals, and I'd argue there are problems with his treatment of the s-block. Not sure what he thinks now. I'd say my preferred approach is an update of this, recognising valent d-orbitals in group 12, and accepting that valence manifolds change down the s-block e.g. adding p from He to Be, or d from Mg to Ca, and asking for only the same number of valence electrons. Basically like what I've previously discussed with you.) Double sharp (talk) 12:33, 9 December 2022 (UTC)
Seems Os2+ is 5d6 after all. Double sharp (talk) 18:18, 13 November 2022 (UTC)
- You are right. It's strange how I missed that. Droog Andrey (talk) 12:00, 15 November 2022 (UTC)
- Thanks for the quick update! :D Double sharp (talk) 12:37, 9 December 2022 (UTC)
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Overly high oxidation states for alkali metals
[edit]If the Cs species are metastable, but the ionisation energies make them unrealistic, then I wonder if they might be prepared by β− decay of Xe fluorides or oxides.
Also, I sent you an email. :) Double sharp (talk) 03:36, 12 December 2022 (UTC)
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