![]() For example, some initial attempts involved investigating chemical reactions under VSC with transition state theory, using simple analytical expressions for the potential energy and dipole moment 22, 23, 27. This is mainly attributed to the complexity of molecule-cavity systems and the lack of promising theoretical tools to disentangle the reaction mechanisms. A series of seminal experimental work have been conducted to monitor reaction pathways and intramolecular vibrational energy redistribution (IVR) process by detecting the IR signature of molecular vibrational polaritons with linear IR spectroscopy and nonlinear two-dimensional IR spectroscopy (2D-IR) 8, 9, 10, 11, 12, 13, 14.ĭespite numerous theoretical efforts trying to reach consensus with experimental measurements, the mechanism by which vibrational strong coupling controls chemical reactions remains obscure 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26. ![]() When the infrared (IR) cavity mode is strongly coupled to specific vibrational excitations, known as vibrational strong coupling (VSC), the molecular vibrational polaritons are formed and shown to potentially alter the chemical reaction and energy transfer pathways 8, 9, 10. Strong light–matter interactions between molecules and the electromagnetic field of an optical cavity have garnered significant interest in the fields of chemistry and materials, as they provide new opportunities to modify chemical reactivity and selectivity 1, 2, 3, 4, 5, 6, 7. While our work focuses on single water dimer system, it provides direct and statistically significant evidence of VSC effects on molecular reaction dynamics. We elucidate the mechanisms behind these effects by investigating the critical role of the optical cavity in modifying the intramolecular and intermolecular coupling patterns. Furthermore, we discover that the cavity surprisingly modifies the vibrational dissociation channels, with a pathway involving both water fragments in their ground vibrational states becoming the major channel, which is a minor one when the water dimer is outside the cavity. We observe that manipulating the light-matter coupling strength and cavity frequencies can either inhibit or accelerate the dissociation rate. In this study, we combine state-of-art quantum cavity vibrational self-consistent field/configuration interaction theory (cav-VSCF/VCI), quasi-classical trajectory method, along with the quantum-chemical CCSD(T)-level machine learning potential, to simulate the hydrogen bond dissociation dynamics of water dimer under VSC. ![]() ![]() Despite numerous experimental and theoretical efforts, the underlying mechanism of VSC effects remains elusive. The vibrational strong coupling (VSC) between molecular vibrations and cavity photon modes has recently emerged as a promising tool for influencing chemical reactivities. ![]()
0 Comments
Leave a Reply. |
AuthorWrite something about yourself. No need to be fancy, just an overview. ArchivesCategories |