Control of Transition‐Metal Cation Reactivity by Electronic State Selection

Chemical Activation of Water Molecule by Collision with Spin–Orbit-State-Selected Vanadium Cation: Quantum-Electronic-State Control of Chemical Reactivity

“…Thus, we expect that by changing the quantum-electronic state is equivalent to altering the electron arrangement of reactant ion and thus can greatly alter its chemical reactivity. It has been speculated for a long while whether different forms of angular momentum states of TM ion can have different effects on chemical reactivity of ions. − The answer to this question requires spin–orbit electronic-state-selected σ measurements for ion–molecule reactions of TM ions, including those of the present study and the most recently reported experiments on the V + (a 5 D J , a 5 F J , and a 3 F J ) + D 2 (CO 2, , CH 4 ) reaction systems. , …”

“…This expectation has been confirmed in recent chemical reactivity studies of the V + (a 5 D J , a 5 F J , and a 3 F J ) + D 2 (CO 2 , CH 4 ) reactions. , The characteristics of low-lying in energy and long lifetimes make it mandatory to account for the chemical reactivity of individual electronic states for any realistic investigations of the bonding and catalytic properties of TM cations. Hence, the capability for performing quantitative chemical reactivity measurements as a function of low-lying electronic state represents a key experimental development, which is expected to provide valuable mechanistic understanding on the chemical reactivity of TM cations. − …”

Self-Reactions in the HBr+ (DBr+) + HBr System: A State-Selective Investigation of the Role of Rotation

“…The majority of data available on IMRs deals with the reaction of cations with neutrals, but reactions of anions with neutrals are of similar importance . Quantum state selectivity has been demonstrated for electronically state-selected ions and for vibrationally state-selected ions. , In general, long-range forces determine the outcome of complex competing channels in IMRs …”

Chemical Activation of a Deuterium Molecule by Collision with a Quantum Electronic State-Selected Vanadium Cation

“…Transition metal (TM) cations are known to play an important role in many research fields, particularly in catalysis. , However, due partly to the complex electronic structures of TM ions, reliable theoretical predictions on chemical reactivity of TM ions toward neutral diatomic and triatomic molecules remain a significant challenge for chemical physicists. , The complex electronic structures of TM ions, manifested as dense manifolds of low-lying electronic states with a variety of spin multiplicities, originate from interactions of valence electrons residing in partially filled d or f subshells. Because of the parity and electron spin selection rules, radiative transitions between these ion electronic states are not allowed, resulting in significantly longer radiative lifetimes for these ion electronic states compared to experimental measurement cycles. − The ability to perform accurate chemical reactivity or integral cross section (σ) measurements of ion–molecule reactions involving TM ions as a function of these low-lying electronic states is believed to be key for fundamental understanding of the distinct bonding and thus catalytic properties possessed by TM ions. − …”