TY - JOUR
T1 - Three-dimensional quantum wave packet study of the Ar-HCl photodissociation
T2 - A comparison between time-dependent self-consistent-field and exact treatments
AU - García-Vela, A.
AU - Gerber, R. B.
PY - 1995
Y1 - 1995
N2 - The time-dependent self-consistent-field (TDSCF) approximation is used to study the photodissociation of the Ar-HCl cluster in a three-dimensional framework. The results are compared with numerically exact quantum calculations, and the properties and accuracy of the TDSCF approach are evaluated on this basis. The TDSCF approximation is used in Jacobi coordinates, and the total wave function is factorized into a wave packet for two coordinates associated with the H atom, and a wave packet for a single coordinate that describes the relative motion of the heavy particles. Quantitative agreement between the TDSCF and the exact results is found for most quantities calculated. The calculations show that photodissociation, and in particular the departure of the H atom is predominantly a direct process, but an appreciable amount of wave packet amplitude moving in excited state resonances is also found. This amplitude seems significantly larger than obtained in recent calculations by Schröder et al. [J. Chem. Phys. 100, 7239 (1994); Chem. Phys. Lett. 235, 316 (1995)]. The validity and computational efficiency of the TDSCF approach for realistic systems of this type is discussed.
AB - The time-dependent self-consistent-field (TDSCF) approximation is used to study the photodissociation of the Ar-HCl cluster in a three-dimensional framework. The results are compared with numerically exact quantum calculations, and the properties and accuracy of the TDSCF approach are evaluated on this basis. The TDSCF approximation is used in Jacobi coordinates, and the total wave function is factorized into a wave packet for two coordinates associated with the H atom, and a wave packet for a single coordinate that describes the relative motion of the heavy particles. Quantitative agreement between the TDSCF and the exact results is found for most quantities calculated. The calculations show that photodissociation, and in particular the departure of the H atom is predominantly a direct process, but an appreciable amount of wave packet amplitude moving in excited state resonances is also found. This amplitude seems significantly larger than obtained in recent calculations by Schröder et al. [J. Chem. Phys. 100, 7239 (1994); Chem. Phys. Lett. 235, 316 (1995)]. The validity and computational efficiency of the TDSCF approach for realistic systems of this type is discussed.
UR - http://www.scopus.com/inward/record.url?scp=0000291360&partnerID=8YFLogxK
U2 - 10.1063/1.470230
DO - 10.1063/1.470230
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AN - SCOPUS:0000291360
SN - 0021-9606
VL - 103
SP - 3463
EP - 3473
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
IS - 9
ER -