Conservation of angular momentum in polyatomic photochemical reactions: H 2 CO(v,J,K a ,K c )yields+HCO(N,K a ,K c ,J)

Abstract

The photodissociation dynamics of the reaction H<SUB>2</SUB>CO + hv yields H + HCO have been investigated just above the reaction threshold. Formaldehyde was excited into specific J, K<SUB>a</SUB>, K<SUB>c</SUB> rotational states of three vibrational levels in the A(<SUP>1</SUP>A<SUB>2</SUB>) state. Molecules in these states undergo internal conversion back to the X (<SUP>1</SUP>A<SUB>1</SUB>) ground state on which the radical fragments are formed. The ensuring distribution of rotational energy in the HCO fragment was measured as a function of the N, K<SUB>a</SUB>, K<SUB>c</SUB> and J equals N +/- S quantum numbers of the fragment, and also the initial v, J, K<SUB>a</SUB>, K<SUB>c</SUB> quantum numbers of the parent. In a previous publication we investigated the dynamics of this reaction at low available energy and concluded that when only the N and K<SUB>a</SUB> quantum numbers of both formaldehyde and the formyl radical are considered, the distributions are modeled well by phase space theory (PST). This is consistent with statistical dynamics on a bound, barrier less surface. Within approximately equals 10 cm<SUP>-1</SUP> of the energetic threshold, a centrifugal barrier affected the populations by inhibiting product states that require large orbital angular momentum. Resolution of K<SUB>c</SUB> in the parent and product gave large deviations from the PST model, however little data were available to quantify this observation. In this work we have extended then umber of initially excited H<SUB>2</SUB>CO levels to explore this 'K<SUB>c</SUB> effect' further. We find that in the HCO K<SUB>c</SUB> state or the lower energy state. This preference is consistent over all N for any particular initial H<SUB>2</SUB>CO state but may very for different initial states. Over the seven initial states probed here, four favored K<SUB>c</SUB> and the other three K<SUB>c</SUB>. A correlation between this K<SUB>c</SUB> preference and the initial state was observed: odd K<SUB>c</SUB> formaldehyde states produce K<SUB>c</SUB> preference in HCO and vice versa for initially even K<SUB>c</SUB> states. A comparison with one previous observation of this effect is presented, however no concrete explanation can be offered at this stage.