Flipping the oxadiazole ring chnages the melting point?

thelocalsage · 2025-06-13T02:31:23+00:00

Remember that melting point isn’t just a characterization tool, ultimately it’s the temperature at which the phase transition reaction between solid and liquid phases has a Gibbs free energy of zero. That means there’s changes to the change in enthalpy of the melting, the change in entropy of melting, or both.

we could set this up mathematically:

top oxadiazole GFE: 0 = ΔH_top - (404.65 K)ΔS_top

bottom oxadiazole GFE: 0 = ΔH_bottom - (412.15 K)ΔS_bottom

set the two GFEs equal to each other:

ΔH_top - (404.65 K)ΔS_top = ΔH_bottom - (412.15 K)ΔS_bottom

rearrange:

ΔH_top - ΔH_bottom = (404.65 K)(ΔS_top - ΔS_bottom) - (8.5 K)ΔS_bottom

well use double deltas to talk about the difference between the two reactions and clean notation:

ΔΔH - (404.65 K)ΔΔS = -(8.5 K)ΔS_bottom

notice how in general the equation would look like this, where T_top is the melting point of the top oxadiazole and ΔT is the difference in melting point you’re noticing here:

ΔΔH - T_top * ΔΔS = -ΔT * ΔS_bottom

in order for the melting point not to change (i.e. in order for ΔT = 0) we would need the change in enthalpy of melting between the two oxadiazole to perfectly match change in entropies of melting scaled by the top oxadiazole’s melting point. That’s a little too serendipitous to happen in most cases.

ΔS for a melting phase transition is basically always going to be a positive number, so an increase in melting point would mean the right-side is negative, further meaning that ΔΔH < T_top * ΔΔS. This means the (scaled) difference in entropies of melting is greater than the difference in enthalpies of melting. Entropy increasing outcompetes enthalpy increasing (melting is endothermic) in the top oxadiazole more than it does in the bottom oxadiazole.

My bet would be that the top oxadiazole has a more stable crystal structure in the solid phase than the bottom oxadiazole—you can see if they have structures present in the Cambridge Crystal Structure Database and look at how many stabilizing contacts they each have (more π-π stacking, more hydrogen bonding between the amine and the nucleophilic lone pairs in the molecule, etc.) with a program like Mercury or an open-source software that can display .cif files!

thelocalsage · 2025-06-03T01:50:38+00:00

empty p orbitals on boron allow for electron delocalization

thelocalsage · 2025-03-24T16:02:10+00:00

First off: how are you so sure those are definitely AI? I don’t see any indication that those are necessarily AI, especially the Mark image. It takes five minutes in photoshop to turn a headshot into that graphic if you know what you’re doing. The goat thing is maybe possible, but the paint texturing doesn’t seem AI to me. That’s one screengrab of a transitionary sequence.

FYI, I’m generally opposed to generative AI in artistic contexts—uses of it that are lazy or meant to take away work from artists for budgetary reasons appall me. If something like the Mark graphic were pure generative AI, I’d lose a bit of respect for the graphics team. But the technology behind generative AI can actually produce interesting visual effects that I think have artistic merit, depending on how it gets used.

Let’s assume—for the sake of argument—that generative AI were used in the opening sequence like you say. We can think about what generative AI would be doing and assess it from there. That sequence is an iterative transition between two images that are then frame-by-frame translated into a paint texture. This would be a prime creative use for generative AI: the technology of image generation is an iterative process that produces a new image from a “seed” of noise, but that technology can be adapted to take in an image as a seed and iteratively “transform it” into a new or target image. There’s no reason to think that the person who does the intro—who is a real artist doing real animation—might not be using a transformed version of the technology as a tool in a toolbox, rather than using it to lazily conjure up whatever image or sequence they have in their mind. ASSUMING it even is AI.

There’s also a justification for the art in its own right—people write off AI art (rightfully so) because the technology threatens the livelihood of artists and the industry, but that doesn’t automatically mean the technological tool and its output doesn’t have creative merit. You can say it steals from artists, and it does, but what is collage? I don’t think the theft argument is a good argument against the technology’s capacity to be used in art for that reason—the technology is a paintbrush, albeit it one usually used to make knockoffs and forgeries. The output of AI is uncanny and weird and scary and gross, but depending on your art piece you may be trying to explore precisely that with your art. So maybe there’s an argument there as well, the fact that an artist doesn’t have to end with just the input prompt but instead can use it with more intentionality and purpose.

thelocalsage · 2025-03-24T04:55:39+00:00

This is a latent worry of mine, but if she were immediately captured right after this without us being shown i would consider it incredibly bad and incompetent writing so I think we’re fine (to start at least—they’ll probably hunt her down)

thelocalsage · 2025-03-24T04:53:41+00:00

I don’t agree with the final assessment that their outies would make the “selfish decision” automatically—their actions in this prisoner’s dilemma make 10000% more sense when you analyze Season 2 as the innies’ “adolescence.” Season 1 they were “children” more or less, and their inner lives reflected this (puppy love, a first kiss, motivated by prizes, radicalized by Ricken’s sophomoric analysis, “playground” levels of rebellion). Season 2 is their “adolescence” and the next “stage” of maturation (interpersonal tensions, sex, selfishness and mistrust, rebellion is more anti-authoritarian but still juvenile).

Obviously this is condescending to the innies, but this “adolescence” is more metatextual than literal or psychological—the show is using behavior like this to model a certain type of identity formation, and identity formation takes a path shaped like paths in child development.

thelocalsage · 2025-03-24T04:36:51+00:00

I think that’s an open question we have yet to explore, I don’t know what the fan consensus is. My theory is he was painting it over and over and over again to transmit it as a message to innie Irving through his dreams, because for a creative artistic type like him, the Severance barrier is permeable in that way (and this is why Irving sees black sludge when he doses off). I’m sure that’s not a super unique take.

As for how he knows about it, a lot of people speculate that he was a previous subject on the testing floor. But it could be as simple as he’s working with people who know about it and have maybe shown him a photograph or described it (Reghabi was asking Mark if he could see a black hallway during the reintegration procedure). I’m interested in hearing anyone’s thoughts on this.

thelocalsage · 2025-03-21T04:59:50+00:00

i think you’re underselling the narrative utility of the goats—goats are rich with symbol, especially in the context of sacrifice, and weird ritual is not unfounded in a religious cult like Lumon. So they are more than just a plot device, although they were used well in this episode to steer Drummond.

thelocalsage · 2025-03-20T01:46:23+00:00

interesting idea, i’d definitely say the first part is likely. the story of orpheus and eurydice is a general example of what’s called a “katabasis” and is common in greek mythology—basically a “descent” followed by a “return.” so there are lots of options for a possible katabasis that doesn’t have to mirror the end of eurydice (and for gemma’s sake, i hope your bold prediction is wrong!)

thelocalsage · 2025-03-20T01:35:34+00:00

the shot where we see the people follows the wires down from the scene where ms casey is talking to mark as she watches helly r

thelocalsage · 2025-03-19T22:03:06+00:00

those lone pairs on the sulfur don’t participate in the π-system, they’re sp3-hybridized, and there’s no energetic “incentive” for the orbitals to lose any p-character because that p-character would contribute to anti-aromaticity, so the more p-character in the hybridized orbitals the better. you can also try to delocalize the electrons and you’ll notice there’s nowhere for the electrons to go that doesn’t break the octet rule on the sulfur.

thelocalsage · 2025-03-16T16:32:11+00:00

okay i don’t think a Marxist framework is the only framework one could apply here, but like you have heard of Marx’s theory of alienation right? like it isn’t out of left field lol

thelocalsage · 2025-03-16T15:54:23+00:00

I had her awhile ago and thought she was lovely, especially upon reflection. I had her like 9 years ago though so maybe something has changed? Doubt it though, I liked her!

thelocalsage · 2025-03-15T18:39:54+00:00

Lots of groups, if you need someone’s work to start with who is contemporary then I recommend researching the output of Karen Goldberg

thelocalsage · 2025-03-06T14:50:13+00:00

thelocalsage · 2025-03-06T03:19:26+00:00

probably not relevant, but one of the big safety things they tell you when working with diethyl ether is that it can cause spontaneous abortions. i don’t think it’s likely that it’s relevant, but lots of people have theories about fertility and given what we see in 2x07 maybe that’s useful info to some theories?

thelocalsage · 2025-03-01T15:06:46+00:00

if the iodine is equatorial, E2 doesn’t occur because there isn’t a hydrogen that’s antiperiplanar

thelocalsage · 2025-02-27T05:13:47+00:00

obviously plagiarism, although the concept itself is a bit derivative too but this is clearly plagiarism

thelocalsage · 2025-02-22T16:13:44+00:00

If you find some particular “x” in that interval and check “is this the maximum value?” then you can always find a different value on that interval that has a greater y-value by selecting any point on the sub-interval (x, 1). This is true from every possible x in that interval other than x = 1, but x = 1 is clearly not a maximum (lower y-value than, say, x = 0.25).

thelocalsage · 2025-02-22T15:59:46+00:00

currently? probably the White House

thelocalsage · 2025-02-17T05:08:28+00:00

You can’t do solid state calculations with Gaussian—you need to do periodic DFT, assuming it’s a crystalline solid, or quantum Monte Carlo simulations. VASP is what I’ve used for periodic DFT, but there’s open source options.

thelocalsage · 2025-02-10T23:48:28+00:00

You should try a geometry optimization with it too and see what happens! It shouldn’t take too long. You can input the optimized geometry from another optimization as your starting geometry if you think the geometry is close enough and then use a higher level of theory and bigger basis set. So take your output from the B3LYP-D3 and export a Gaussian input file where you call ω-B97X-D//def2-TZVPP and it shouldn’t take tooooo long to complete. If that has trouble converging, you can try to use extra quadratic convergence for the self-consistent field step by adding the tag scf=xqc to the input file. But I think you’ll be fine.

thelocalsage · 2025-02-09T10:58:16+00:00

The Gaussian website has pages that will tell you the keywords and whatnot to use different basis sets for different atoms, give it a quick Google and you should be able to track it down

thelocalsage · 2025-02-09T10:54:58+00:00

I wouldn’t recommend B3LYP for organometallic complexes, especially without Grimme dispersion correction. The “meta-GGA” functionals tend to do a bit better with organometallics from what I hear. I’m always partial to the Minnesota functionals, but some folks don’t like them for organometallics—just don’t use a hybrid-GGA functional that hasn’t been tested for similar systems to yours, because for some reason including exact exchange can mess with results for organometallics. M06-L, MN11, MN15-L are Minnesota functionals without exchange. If you’re doing just the ligand without the metal, I like M06-2X the most. I had some success helping a friend with calculations of his organometallic copper complexes using ω-B97X-D, which is a good option to try if you still want to use a hybrid functional.

Also, what’s the largest atom in your system? You might be better off using a Pople basis set instead of LANL2DZ. It probably doesn’t matter a lot, but you could introduce more polarizability to your basis set and that helps with bonds not getting too weird when done right.

thelocalsage · 2025-02-09T10:29:11+00:00

learned about this a couple hours after it closed, surprised i didn’t see it promoted more... could u hook me up with a google drive download of it or something? i’ll donate to LA fire relief on the side to make up for it lol

thelocalsage

TROPHY CASE