Photodissociation of HOD (νOD=3): Demonstration of preferential O–D bond breaking

Abstract

Selective OD bond dissociation of HOD: Photodissociation of vibrationally excited HOD in the 5 ν O D state

Photodynamic control using field optimized initial state: A mechanistic investigation of selective control with application to IBr and HI photodissociation

“…1 While the focus of these theoretical approaches has been on field design, the photodissociation yield has also been found to be extremely sensitive to the initial vibrational state from which photolysis is induced. Examples include the photodissociation of H 2 ϩ , 13 D 2 ϩ , 14 HI, 15,16 HOD, 6,17,18 and HCl 19 in each of which the product yield has been found to be sensitive to the initial vibrational state of the molecule. Since the initial vibrational state which is subjected to photolysis is critical in determining the photodissociation products, it is reasonable to expect an appropriately optimized linear superposition of these vibrational eigenstates to serve as a better initial condition for selective maximization of the desired product.…”

Initial state laser control of curve-crossing reactions using the Rayleigh–Ritz variational procedure

“…This vibrationallymediated photodissociation technique has been exploited in bond-selective photodissociation of HOD where the relative yields of the resulting products ͑HϩOD or OHϩD͒ can be controlled to a large degree through selective IR excitation of certain vibrational modes of the ground surface before application of the UV photodissociation pulse. [12][13][14][15] Also, a theoretical control study has been presented for the HOD system where a non-stationary vibrational state is prepared with an intense IR pulse and then subsequently dissociated with a weak UV pulse. 16 Like the studies mentioned above, our control method of photodissociation reactions is through manipulation of the vibrational states prior to application of the photodissociation pulse.…”

Communication: Mode-specific photodissociation of vibrationally excited pyrrole

“…17 On the other hand, excitation of the second OD stretching overtone (3ν OD ) state was required to obtain preferential OD bond fission. 18 These results indicated that localization of energy is a necessary but not sufficient condition, implying that favorable Franck-Condon (FC) factors, namely, overlap integrals between the prepared intermediate vibrational states on the ground electronic state and those on the excited state, carrying the same character of vibrational motion, were crucial for obtaining bond-selectivity.…”

“…12 Excitation in a specific vibrational mode and, moreover, localization and preservation of energy until the excited molecule interacts with photons, could be foreseen for small molecules. Indeed, since the pioneering theoretical predictions [13][14][15] on photodissociation of vibrationally excited water with a single deuterium label, HOD, intensive experimental studies [16][17][18][19][20] were performed in attempt to control product identity or to obtain enhanced reactivity. For example, it has been shown that the OH bond dissociation is largely enhanced by dissociating HOD initially excited with four OH stretch quanta.…”