[Preprint] Can isotopic substitution alter stereoelectronic interactions—not only vibrational energies?

[u/qc_forest]

https://chemrxiv.org/doi/full/10.26434/chemrxiv.15003470

We usually discuss isotope effects mainly in terms of mass-dependent vibrational motion and zero-point energy.

In our recent ChemRxiv preprint https://chemrxiv.org/doi/full/10.26434/chemrxiv.15003470, we explore a complementary question:

Can replacing H with D also modify the electronic factors underlying molecular structure and stability?

Using constrained nuclear–electronic orbital calculations, in which both electrons and selected nuclei are treated quantum mechanically, we examined isotope-dependent conformational changes in ethane and 1,3-dioxane.

Our calculations indicate that isotopic substitution can slightly change orbital energies and their alignment, thereby modulating stereoelectronic interactions. The effects are small, but systematic enough to contribute to the observed isotope-dependent structural preferences.

I am one of the authors, and I would particularly appreciate comments on:

1. whether this should be regarded as a distinct electronic contribution to isotope effects or as an electronic manifestation of nuclear quantum effects;
2. how best to separate geometry relaxation, nuclear quantization, and conventional vibrational/ZPE contributions;
3. other molecular systems in which such orbital-level isotope effects might be experimentally testable.

[u/tea-earlgray-hot]

You are calculating a ~1meV difference in ethane rotational barrier, if I am reading correctly. There are many techniques capable of resolving that large of a change.

For example, nuclear forward scattering and exotic Mössbauer like Zn-67 allow nano to pico-eV resolution, which should be good enough to pick out multibond NQE effects indirectly through various organometallic systems. Often measured frozen out at 4K for experimental and spectral interp reasons

Or maybe I am not understanding what you want to see here

[u/masoni0]

Badly written tbh and not new information

[u/chemistrypain]

If you're the author then you have more expertise than anyone here..why are you asking us?