I know you said she’s a very experienced cyclist, but is it possible she’s afraid to take her hands off the bars? I realized my wife had picked cute bottle holders that squeeze too tight and made it very hard to pull out the bottle. We switched to arundel side entry and it REALLY helped with her confidence in being able to ride and remove/insert the bottle while pedaling. She still won’t eat though, so I stop every 45 minutes or so to chat and take pics while she eats.
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There is a high probability that your wife is smaller than you, this her total calorie and water needs are less than yours.
There is also a large variation between individuals in glycogen reserves/ability to utilize fat for a given power output, and ability to retain water. Less trained people sweat less than more trained people.
Even in equally trained individuals, there is a huge variation in hourly sweat volume, like by a factor of 4 or more (ie: 0.5 to 2L per hour under equivalent conditions).
As a result, consider that while she probably needs to at least drink more based on your description, you really can’t use your own consumption rates as any sort of valid comparison.
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Going to toss out a completely random psychology 101 thought. Maybe her idea of you caring about her well being doesn’t involve the bike 
FWIW I’ve been married a long time and still misjudge a lot of her verbal and non-verbal cues. My wife isn’t looking for my help / problem solving, she is looking for emotional support. And when I push solutions it only creates a wall and animosity. Not saying thats whats going on here, but worth thinking about. FWIW.
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Key is ask why. Then ask why to whatever she says. Then ask why to that too.
Maybe first ask if she even wants to talk about it though.
Bingo.
@ellotheth, my wife is a cat 1 roadie, triathlete, and sport dietitian, and all the things you list are relevant and our experience is virtually identical to you and your husband’s, even though she’s worlds fitter than me.
All that you listed still very much apply to her.
@bobw, It’s definitely worth carefully asking why, when you’re off and away from the bike.
From there you can drill down into and troubleshoot each individual reason, if she’s interested. It seems likely, that there will be an interplay between barriers to consumption and desire not to consume, which, all told, result in vastly under-consuming compared to what is optimal for performance.
Fair warning, if you’d like to stay married, approach with more gentleness, understanding and empathy than you think you need. You’ll still need more 
Approaching the topic while she’s hypoglycemic and possibly hangry, is probably suboptimal. Amiright @michelleihowe?? 
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@KiloCal - she does the same whether she’s with me, with the club or on her own so the pressure of “staying on my wheel” may be part of it while she’s with me it can’t be whilst she’s on her own at self-selected pace, etc. She’s a top tube bag on her road bike for snacks.
@Pbase - she’s happy removing a bottle from the cage, drinking from it and putting it back whilst riding along, either on road or off-road.
@cnidos - yes she’s smaller and lighter but she’s not 80% smaller and lighter! Away from the bike she’s a healthy appetite, it’s quite possible that there’s some exercise induced appetite suppression going on.
I’ve a feeling she just gets fixated on the riding and drinking/eating is seen as a distraction from that rather than an aid.
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I will point out that sweating sooner and more copiously during exercise, as you’ve suggested happens, means that less trained people sweat less than more trained people… 
Taking an untrained person and getting them to start exercising increases their sweat volume by around 10-20% (Water Requirements During Exercise in the Heat - Nutritional Needs in Hot Environments - NCBI Bookshelf). Not a huge amount given the 4x difference (or more) between individual people, but still another factor to consider.
As you mention in your comment, it’s likely related to sweating sooner during exercise (onset of sweat production beginning at a lower temperature trigger), and more copiously for a given effort (ex: Effects of exercise training on thermoregulatory responses and blood volume in older men - PubMed)
This is like me. I can even take bags of Haribos or other things I really like, and forget about them until I get home. Then will nail them all off the bike some other day…
I’m a bit better with drinking, at least when it’s not cold, so trying to have carbs in my drinks.
However, I usually don’t feel like eating or not eating makes a big difference. Maybe that’s part of the answer to your question - I’ll describe how it feels to me, because maybe it’s the same for her. I can easily do 3 hours without food/drink, and I very rarely bonk “hard”. After about 3 hours I think I enter some sort of “slow bonk”. RPE/breathing goes up, so even though I can keep power up, it feels harder (so climbing slower makes sense). But I can keep riding, just slower. I also don’t have much appetite once home, this usually only happens a day or so later. On the other hand, I don’t get much of a boost from eating either - quite often, food only makes me feel full and sluggish. I have no idea how people talk about getting a boost from sugar, or feelimg hyper - I can eat a ton of sugar and nothing happens. I also struggle to carb load - no issues eating tons of carbs, I do that anyway, but it doesn’t do anything obvious for my performance, and often just makes me feel full and heavy.
Think the combinations of these two things - not feeling an obvious drop in performance (it’s more slow and gradual), and on the other hand feeling like food mostly makes you feel full, and not give you a boost or anything, makes it easy to forget about eating.
Just to clarify - I think food prevents the “slow bonk”, but it’s not an obvious change or anything.
Don’t tell her.
Now what was the question?
Now I’ve read your post, I can confidently refer you back to my first post 
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Hang on.
She rode 145km/90mi over 8 hours on half a liter of water, 1 bar, and lunch break?
The lady’s got some serious endurance and is probably fully adapted to fat burning. The hydration is what it is.
Staying in Z1/Z2. Seems to work for her.
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4 hours to the halfway point!
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Isn’t that what they said?
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Normal summer club ride that. Honestly a lot of my club would do that. Maybe a banana instead of a bar.
Yeah there were some double negatives in there. Was not super clear.
Do you know whether anyone else in your wife’s ride group in your club has similar issues? Could you get a nutritionist or coach to come and do a talk for your club to address the topic in general and encourage them all to support each other to improve their hydration and nutrition on the bike?
My wife is not confident eating or drinking on the fly, so she never takes in enough fluids or food. She is a good cyclist but not a good bike handler, and has had one really bad crash (concussion, broken wrist), so is reluctant to take one hand, let alone two, off the bars.
I would schedule a “lunch” stop if you are going to ride together. Find a picnic table or take along a tiny packable picnic blanket (I have one that’s the size of a double deck of cards) and take 30 minutes or so. That would also settle her stomach so she feels hungry.
I think the last thing someone wants is an “intervention”.
Tandems are great for addressing this sort of thing.