TY - JOUR
T1 - Noncovalently bound molecular complexes beyond diatom-diatom systems
T2 - full-dimensional, fully coupled quantum calculations of rovibrational states
AU - Felker, Peter M.
AU - Bačić, Zlatko
N1 - Publisher Copyright:
© 2022 The Royal Society of Chemistry.
PY - 2022/10/4
Y1 - 2022/10/4
N2 - The methodological advances made in recent years have significantly extended the range and dimensionality of noncovalently bound, hydrogen-bonded and van der Waals, molecular complexes for which full-dimensional and fully coupled quantum calculations of their rovibrational states are feasible. They exploit the unexpected implication that the weak coupling between the inter- and intramolecular rovibrational degrees of freedom (DOFs) of the complexes has for the ease of computing the high-energy eigenstates of the latter. This is done very effectively by using contracted eigenstate bases to cover both intra- and intermolecular DOFs. As a result, it is now possible to calculate rigorously all intramolecular rovibrational fundamentals, together with the low-lying intermolecular rovibrational states, of complexes involving two small molecules beyond diatomics, binary polyatomic molecule-large (rigid) molecule complexes, and endohedral complexes of light polyatomic molecules confined inside (rigid) fullerene cages. In this Perspective these advances are reviewed in considerable depth. The progress made thanks to them is illustrated by a number of representative applications. Whenever possible, direct comparison is made with the available infrared, far-infrared, and microwave spectroscopic data.
AB - The methodological advances made in recent years have significantly extended the range and dimensionality of noncovalently bound, hydrogen-bonded and van der Waals, molecular complexes for which full-dimensional and fully coupled quantum calculations of their rovibrational states are feasible. They exploit the unexpected implication that the weak coupling between the inter- and intramolecular rovibrational degrees of freedom (DOFs) of the complexes has for the ease of computing the high-energy eigenstates of the latter. This is done very effectively by using contracted eigenstate bases to cover both intra- and intermolecular DOFs. As a result, it is now possible to calculate rigorously all intramolecular rovibrational fundamentals, together with the low-lying intermolecular rovibrational states, of complexes involving two small molecules beyond diatomics, binary polyatomic molecule-large (rigid) molecule complexes, and endohedral complexes of light polyatomic molecules confined inside (rigid) fullerene cages. In this Perspective these advances are reviewed in considerable depth. The progress made thanks to them is illustrated by a number of representative applications. Whenever possible, direct comparison is made with the available infrared, far-infrared, and microwave spectroscopic data.
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U2 - 10.1039/d2cp04005k
DO - 10.1039/d2cp04005k
M3 - Review article
C2 - 36214258
AN - SCOPUS:85140416644
SN - 1463-9076
VL - 24
SP - 24655
EP - 24676
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 40
ER -