On the conformational memory in the photodissociation of formic acid.
The photodissociation of formic acid at 248 and 193 nm was investigated by classical trajectory and RRKM calculations using an interpolated potential energy surface, iteratively constructed using the B3LYP/aug-cc-pVDZ level of calculation. Several sampling schemes in the ground electronic state were employed to explore the possibility of conformational memory in formic acid. The CO/CO2 branching ratios obtained from trajectories initiated at the cis and at the trans conformers are almost identical to each other and in very good accordance with the RRKM results. In addition, when a specific initial excitation that simulates more rigorously the internal conversion process is used, the calculated branching ratio does not vary with respect to those obtained from cis and trans initializations. This result is at odds with the idea of conformational memory in the ground state proposed recently for the interpretation of the experimental results. It was also found that the calculated CO vibrational distributions after dissociation of the parent molecule at 248 nm are in agreement with the experimental available data.
Martínez-Núñez
E
E
Departamento de Química Física, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain. qfemilio@usc.es
Vazquez
S A
SA
Borges
I
I
Rocha
A B
AB
Estévez
C M
CM
Castillo
J F
JF
Aoiz
F J
FJ