Vibrational Relaxation and Bond Dissociation in Methylpyrazine on Collision with N2 and O2
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The present study uses quasi-classical trajectory procedures to examine the vibrational relaxation and dissociation of the methyl and ring C–H bonds in excited methylpyrazine (MP) during collision with either N2 or O2. The energy-loss (–ΔE) of the excited MP is calculated as the total vibrational energy (ET) of MP is increased in the range of 5,000 to 40,000cm –1. The results indicate that the collision-induced vibrational relaxation of MP is not large, increasing gradually with increasing ET between 5,000 and 30,000 cm–1, but then decreasing with the further increase in ET. In both N2 and O2 collisions, the vibrational relaxation of MP occurs mainly via the vibration-to-translation (V→T) and vibration-to-vibration (V→V) energy transfer pathways, while the vibration-to-rotation (V→R) energy transfer pathway is negligible. In both collision systems, the V→T transfer shows a similar pattern and amount of energy loss in the ET range of 5,000 to 40,000cm–1, whereas the pattern and amount of energy transfer via the V→V pathway differs significantly between two collision systems. The collision-induced dissociation of the C–Hmethyl or C–Hring bond occurs when highly excited MP (65,000–72,000 cm–1) interacts with the ground-state N2 or O2. Here, the dissociation probability is low (10–4–10–1), but increases exponentially with increasing vibrational excitation. This can be interpreted as the intermolecular interaction below ET = 71,000 cm−1. By contrast, the bond dissociation above ET = 71,000 cm−1 is due to the intramolecular energy flow between the excited C–H bonds. The probability of C–Hmethyl dissociation is higher than that of C–Hring dissociation.
Abstract
The present study uses quasi-classical trajectory procedures to examine the vibrational relaxation and dissociation of the methyl and ring C–H bonds in excited methylpyrazine (MP) during collision with either N2 or O2. The energy-loss (–ΔE) of the excited MP is calculated as the total vibrational energy (ET) of MP is increased in the range of 5,000 to 40,000cm –1. The results indicate that the collision-induced vibrational relaxation of MP is not large, increasing gradually with increasing ET between 5,000 and 30,000 cm–1, but then decreasing with the further increase in ET. In both N2 and O2 collisions, the vibrational relaxation of MP occurs mainly via the vibration-to-translation (V→T) and vibration-to-vibration (V→V) energy transfer pathways, while the vibration-to-rotation (V→R) energy transfer pathway is negligible. In both collision systems, the V→T transfer shows a similar pattern and amount of energy loss in the ET range of 5,000 to 40,000cm–1, whereas the pattern and amount of energy transfer via the V→V pathway differs significantly between two collision systems. The collision-induced dissociation of the C–Hmethyl or C–Hring bond occurs when highly excited MP (65,000–72,000 cm–1) interacts with the ground-state N2 or O2. Here, the dissociation probability is low (10–4–10–1), but increases exponentially with increasing vibrational excitation. This can be interpreted as the intermolecular interaction below ET = 71,000 cm−1. By contrast, the bond dissociation above ET = 71,000 cm−1 is due to the intramolecular energy flow between the excited C–H bonds. The probability of C–Hmethyl dissociation is higher than that of C–Hring dissociation.
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