Strong-field ionization of polyatomic molecules: ultrafast H atom migration and bond formation in the photodissociation of CH₃OH

Abstract

Strong-field ionization induces various complex phenomena like bond breaking, intramolecular hydrogen migration, and bond association in polyatomic molecules. The H-atom migration and bond formation in CH3OH induced by intense femtosecond...

Strong-field ionization of CH3Cl: proton migration and association

“…46,47 The same level of theory has previously also produced reliable and accurate results by supporting the experimentally observed results for dissociation processes. 3 In order to understand the intramolecular hydrogen migration process in CH 3 Cl 2+ , four different pathways were designed and then further computed on the CH 3 Cl 2+ PES in which CH 3 Cl 2+ can be dissociated into multiple fragments. Furthermore, vibrational frequencies were computed at the same level of theory (M06-2X/6-311++G(d,p)) to confirm that the resulting geometries correspond to minima or TSs on the PES and to attain zero-point energies.…”

“…This phenomenon, known as strong-field ionization (SFI), has been studied in atoms and molecules for many decades. [1][2][3] The large number of degrees of freedom in molecules, along with the coupling of the electronic and nuclear motions, renders the understanding of light-induced ultrafast processes in molecules extremely challenging. Once a molecule is ionized, it is transferred from the ground state to either a ground or excited ionic state.…”

“…4,5 H 3 + formation involves intramolecular proton migration, 6,7 is complex and has been studied in many hydrocarbons. 3,[8][9][10] In recent studies, it has been found to be a two-step process. The first step involves the double ionization of the molecule, followed by the breakup of two C-H bonds and the formation of a neutral H 2 molecule.…”

“…3 Cl cations, dications, and all highly charged ions. The H + yield is 10 times lower than the CH 3 Cl + yield up to 8 Â 10 13 W cm À2 .…”